Amino-acid amide derivatives, agricultural or horticultural fungicides, and method for producing the same

ABSTRACT

The present invention provides an agricultural or horticultural fungicide including an effective amount of an amino-acid derivative represented by the formula: ##STR1## wherein R 1  represents a lower alkyl group (optionally having at least one same or different substituent of a halogen atom, an alkoxy group, and a cyano group), R 2  represents an ethyl group, or an n-propyl group, R 3  represents a hydrogen atom or a lower alkyl group, R 4  represents a hydrogen atom, R 5 , R 6 , and R 7  independently represent a hydrogen atom or a lower alkyl group, R 8  represents a hydrogen atom, or a lower alkyl group, Z 1  and Z 2  independently represent an oxygen atom or a sulfur atom, Z 3  represents an oxygen atom, or a sulfur atom, Q represents a phenyl group, m represents an integer from 0 to 2, and n represents 0 or 1. 
     The amino-acid amide derivatives according to the present invention exhibit superior control of cucumber downy mildew (Pseudoperonospora cubensis), tomato late blight (Phytophthora infestans), and grape downy mildew (Plasmopara viticola), and are effective for potato late blight (Phytophthora infestans). In addition, the agricultural or horticultural fungicides of the present invention are also characterized in that they are not harmful chemicals and exhibit excellent characteristics such as systemic action, residual activity, and persistence after rain-fall.

FIELD OF THE INVENTION

The present invention relates to an amino-acid amide derivative as wellas to an agricultural or horticultural fungicide containing the same asan active ingredient. The present invention also relates to a processfor preparing the same.

BACKGROUND OF THE ART

Amino-acid amide derivatives have been disclosed as intermediates formedicines in Japanese Patent Application, First Publication Nos. Sho56-8352 and Sho 62-89696. However, these documents fail to disclose theutility of the amino-acid amide derivatives. Although Japanese PatentApplication First Publication Nos. Hei 3-5451, Hei 3-153657, Hei4-230652, Hei 4-230653, Hei 4-283554, Hei 4-308507, and Hei 4-338372disclose that some amino-acid amides are useful for biocides, thecompounds disclosed in these documents are different from the amino-acidamide derivatives according to the present invention.

DISCLOSURE OF THE INVENTION

The present inventors have synthesized various amino-acid amidederivatives and have carried out extensive research in connection withtheir effects on the physiological activities of fungi. As a result, wehave found that the compounds according to the present invention exhibita broad spectrum of anti-fungal activity especially against cucumberdowny mildew, grape downy mildew, and tomato late blight, and at thesame time they do not hinder desirable plant growth.

According to an aspect of the present invention, there is provided anamino-acid amide derivative represented by the formula: ##STR2## whereinR¹ represents a lower alkyl group (optionally having at least one sameor different substituent selected from the group consisting of a halogenatom, an alkoxy group, and a cyano group),

a lower alkenyl group,

a lower alkynyl group,

a cycloalkyl group (optionally having at least one same or differentsubstituent selected from the group consisting of methyl group and ahalogen atom),

a cycloalkylalkyl group,

a cycloalkenyl group,

an alkylene oxide group,

an aralkyl group (optionally having at least one same or differentsubstituent selected from the group consisting of a methyl group, acyano group, and a nitro group),

a phenyl group (optionally having at least one same or differentsubstituent selected from the group consisting of a halogen atom,

a lower alkyl group which may be substituted with a same or differenthalogen atom,

a lower alkoxy group which may be substituted with a same or differenthalogen atom,

a cyano group, and

a nitro group), or

a heterocyclic group,

R² represents an ethyl group, an n-propyl group, an isopropyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, an alkenyl group,a cycloalkyl group, a phenyl group (optionally having at least onesubstituent of halogen atom),

R³ represents a hydrogen atom or a lower alkyl group,

R⁴ represents a hydrogen atom, a lower alkyl group, or a cyano group,

R⁵, R⁶, and R⁷ independently represent a hydrogen atom or a lower alkylgroup,

R⁸ represents a hydrogen atom, a lower alkyl group, an aralkyl group, aphenyl group, an alkoxycarbonyl group, or a cyano group,

Z¹ and Z² independently represent an oxygen atom or a sulfur atom,

Z³ represents an oxygen atom, a sulfur atom, a group N--R¹⁰ (wherein R¹⁰represents a hydrogen atom, a methyl group, a methylcarbonyl group, aphenylcarbonyl group, a methoxycarbonyl group, or a methoxymethylgroup), a sulfinyl group, a sulfonyl group, a group COO, a group CONR¹¹(wherein R¹¹ represents a hydrogen atom or a lower alkyl group),

Q represents

a phenyl group [optionally having at least one same or differentsubstituent selected from the group consisting of

a halogen atom,

a lower alkyl group which may be substituted with at least one same ordifferent halogen atom,

a lower alkoxy group which may be substituted with a same or differenthalogen atom,

a cyano group,

a nitro group,

a lower alkoxycarbonyl group,

a methylsulfonyl group,

a methylsulfinyl group,

a methylthio group which may be substituted with a halogen atom,

a dimethylamino group,

a phenylsulfonyl group,

an acyl group, and a phenyl group],

an alkylene oxide group,

a heterocyclic group (optionally having a substituent selected from thegroup consisting of a halogen atom, an alkyl group, a trifluoromethylgroup, and a nitro group), or

a condensed heterocyclic group optionally having a substituent selectedfrom the group consisting of a halogen atom and a nitro group,

m represents an integer from 0 to 2, and

n represents 0 or 1, and an agricultural or horticultural fungicidecontaining the same as the active ingredient.

The terms employed in the present invention are defined as follows. Theterm "alkyl group" is used herein to mean a straight or branched alkylgroup possessing 1 to 6 carbon atoms including, but not limited to, amethyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, sec-butyl group, tert-butyl group, n-pentylgroup, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group,2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 1-ethylpropyl group,n-hexyl group, or the like.

The term "halogen atom" is used herein to mean a fluorine atom, chlorineatom, bromine atom, or iodine atom.

The term "lower alkenyl group" is used herein to mean a straight orbranched alkenyl group possessing 2 to 6 carbon atoms and including, butnot limited to, a vinyl group, 1-propenyl group, 2-propenyl group,isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group,1-methyl-1-propenyl group, 2-methylpropenyl group, 1-ethylvinyl group,or the like.

The term "lower alkynyl group" is used herein to mean a straight orbranched alkynyl group possessing 2 to 6 carbon atoms and including, forexample, an ethynyl group, propynyl group, butynyl group,1-methyl-2-propynyl group, or the like.

The term "cycloalkyl group" is used herein to mean a cycloalkyl grouppossessing 3 to 8 carbon atoms and including, but not limited to, acyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexylgroup, cycloheptyl group, or the like.

The term "cycloalkenyl group" is used herein to mean a cycloalkenylgroup possessing 4 to 8 carbon atoms and including, for example, acyclobutenyl group, cyclopentenyl group, cyclohexenyl group,cycloheptenyl group, or the like.

The term "aralkyl group" is used herein to mean an aralkyl grouppossessing 7 to 8 carbon atoms and including, but not limited to, abenzyl group, phenethyl group, or the like.

The term "alkylene oxide group" is used herein to mean an alkylene oxidegroup possessing 2 to 6 carbon atoms and including, for example, anoxiranyl group, oxetanyl group, tetrahydrofuranyl group,tetrahydropyranyl group, or the like.

The preferred compounds of the present invention are represented byformula [I], wherein R¹ represents a straight or branched alkyl grouppossessing 2 to 6 carbon atoms, a straight or branched alkenyl grouppossessing 3 carbon atoms, a cycloalkyl group possessing 5 to 6 carbonatoms, or a phenyl group optionally having a substituent; R² representsan ethyl group, an n-propyl group, an isopropyl group, or a sec-butylgroup; R³ represents a hydrogen atom or a methyl group; R⁴ represents ahydrogen atom or a methyl group; R⁵ represents a hydrogen atom or amethyl group; R⁶ represents a hydrogen atom or a methyl group; Qrepresents a phenyl group optionally having a substituent; m representsan integer of 0 or 1; n represents 0; Z¹, Z², and Z³ represent an oxygenatom or a sulfur atom; and the amino acid is an L-isomer.

The compounds represented by formula [I] according to the presentinvention can exist in stereoisomers by virtue of the presence of two ormore chiral centers. The present invention relates to all suchstereoisomers, including diastereomers, enantiomers, and mixturesthereof, which can be separated by appropriate methods.

Next, the compounds represented by formula [I] according to the presentinvention are listed in Tables 1 to 12. However, it should be understoodthat the invention is not limited to these compounds. The compoundNumbers given in Tables 1 to 12 will be referred to in the subsequentdescription.

In Tables 1 to 12, Compound Nos. 108, 433, 456, 459, 460, 461, 462, 464,467, 470, 471,472, and 475 possess D,L-configurational amino acidmoieties; Compound No. 109 possesses a D-configurational amino acidmoiety; Compound Nos. 233, 234, 235, 236, 237, 238, 425, 426, 427possess (2S)-butyric acid moieties; and the compounds other than thecompounds described above possess L-configurational amino acid moieties.Compound Nos. 33, 345, and 346; Compound Nos. 107, 116, and 117;Compound Nos. 135, 395, and 396; Compound Nos. 228, 414, and 415; andCompound Nos. 452, 453, and 454 are mixtures of diastereomers, and arealso individual diastereomers. In addition, Compound Nos. 26 and 27;Compound Nos. 45 and 356; Compound Nos. 335 and 336; Compound Nos. 397and 401; and Compound Nos. 409 and 410 are mixtures of diastereomers,and are also one of the individual diastereomers, respectively. CompoundNo. 108 is a mixture of four isomers and Compound No. 433 is a mixtureof two isomers. Compound Nos. 483 to 501,504, 505, 510 to 518, 521, and522 are L-Val-DL-Ala; Compound Nos. 502, 503, 508, 509, 519, and 525 areL-Val-D-Ala; Compound No. 520 is L-Val-L-Ala; Compound Nos. 506 and 523are L-Ile-D-Ala; Compound No. 526 is L-Val-Gly; and Compound Nos. 507and 524 are (2S)-butylyl-D-Ala.

In the tables of the present specification, the expressions "C₃ H₇ -i","C₄ H₉ -t", "C₄ H₉ -s", and "C₄ H₉₋ i" are used to indicate an isopropylgroup, a tert-butyl group, a sec-butyl group, and an isobutyl group,respectively.

                                      TABLE 1                                     __________________________________________________________________________     ##STR3##                                                                     Com-                                                 Melting Point            pound                                                (°C.) or                                                               Reflactive               No. R.sup.1       R.sup.9                                                                          Z.sup.1                                                                         Z.sup.2                                                                         Z.sup.3   A                 Index (n.sub.D                                                                .sup.20)                 __________________________________________________________________________     1  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR4##         88-92                     2  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR5##          98-100                   3  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR6##         1.5051                    4  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR7##         97-98                     5  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR8##         77-80                     6  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR9##         1.5051                    7  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR10##         99-101                   8  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR11##        86-89                     9  C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR12##        1.4899                    10 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR13##        86-89                     11 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR14##                                  12 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR15##        83-87                     13 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR16##        53-56                     14 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR17##        1.5081                    15 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR18##        112-114                   16 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR19##        105-107                   17 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR20##        95-97                     18 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR21##        89-92                     19 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR22##        85-89                     20 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR23##         99-100                   21 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR24##        102-104                   22 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR25##        87-91                     23 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR26##        88-90                     24 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR27##         98-103                   25 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR28##        120-125                   26 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR29##        108-110                   27 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR30##        143-146                   28 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR31##        115-117                   29 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR32##        94-98                     30 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR33##                                  31 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR34##                                  32 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR35##                                  33 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR36##        149-152                   34 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR37##                                  35 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR38##                                  36 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR39##                                  37 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR40##                                  38 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR41##                                  39 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR42##                                  40 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR43##                                  41 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR44##                                  42 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR45##        149-152                   43 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR46##                                  44 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR47##                                  45 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR48##        not determined            46 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR49##                                  47 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR50##                                  48 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR51##                                  49 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR52##                                  50 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR53##                                  51 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR54##                                  52 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR55##                                  53 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR56##                                  54 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR57##        112-115                   55 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR58##                                  56 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR59##                                  57 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         O O O                                                                                        ##STR60##                                  58 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR61##                                  59 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR62##                                  60 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR63##                                  61 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR64##                                  62 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR65##                                  63 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR66##        140-143                   64 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR67##                                  65 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR68##                                  66 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR69##                                  67 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR70##                                  68 C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR71##                                  69                                                                                ##STR72##    CH.sub.3                                                                         O O O                                                                                        ##STR73##                                  70                                                                                ##STR74##    CH.sub.3                                                                         O O O                                                                                        ##STR75##                                  71                                                                                ##STR76##    CH.sub.3                                                                         O O O                                                                                        ##STR77##                                  72                                                                                ##STR78##    CH.sub.3                                                                         O O O                                                                                        ##STR79##                                  73                                                                                ##STR80##    CH.sub.3                                                                         O O O                                                                                        ##STR81##                                  74                                                                                ##STR82##    CH.sub.3                                                                         O O O                                                                                        ##STR83##                                  75                                                                                ##STR84##    CH.sub.3                                                                         O O O                                                                                        ##STR85##                                  76                                                                                ##STR86##    CH.sub.3                                                                         O O O                                                                                        ##STR87##                                  77                                                                                ##STR88##    CH.sub.3                                                                         O O O                                                                                        ##STR89##        82-86                     78                                                                                ##STR90##    CH.sub.3                                                                         O O O                                                                                        ##STR91##                                  79                                                                                ##STR92##    CH.sub.3                                                                         O O O                                                                                        ##STR93##                                  80                                                                                ##STR94##    CH.sub.3                                                                         O O O                                                                                        ##STR95##                                  81                                                                                ##STR96##    CH.sub.3                                                                         O O O                                                                                        ##STR97##                                  82                                                                                ##STR98##    CH.sub.3                                                                         O O O                                                                                        ##STR99##                                  83                                                                                ##STR100##   CH.sub.3                                                                         O O O                                                                                        ##STR101##                                 84                                                                                ##STR102##   CH.sub.3                                                                         O O O                                                                                        ##STR103##                                 85                                                                                ##STR104##   CH.sub.3                                                                         O O O                                                                                        ##STR105##                                 86                                                                                ##STR106##   CH.sub.3                                                                         O O O                                                                                        ##STR107##                                 87                                                                                ##STR108##   CH.sub.3                                                                         O O O                                                                                        ##STR109##                                 88                                                                                ##STR110##   CH.sub.3                                                                         O O O                                                                                        ##STR111##       145-148                   89                                                                                ##STR112##   CH.sub.3                                                                         O O O                                                                                        ##STR113##                                 90                                                                                ##STR114##   CH.sub.3                                                                         O O O                                                                                        ##STR115##                                 91                                                                                ##STR116##   CH.sub.3                                                                         O O O                                                                                        ##STR117##                                 92                                                                                ##STR118##   CH.sub.3                                                                         O O O                                                                                        ##STR119##                                 93                                                                                ##STR120##   CH.sub.3                                                                         O O O                                                                                        ##STR121##                                 94                                                                                ##STR122##   CH.sub.3                                                                         O O O                                                                                        ##STR123##                                 95                                                                                ##STR124##   CH.sub.3                                                                         O O O                                                                                        ##STR125##                                 96                                                                                ##STR126##   CH.sub.3                                                                         O O O                                                                                        ##STR127##                                 97                                                                                ##STR128##   CH.sub.3                                                                         O O O                                                                                        ##STR129##       158-162                   98                                                                                ##STR130##   CH.sub.3                                                                         O O O                                                                                        ##STR131##       123-126                   99                                                                                ##STR132##   CH.sub.3                                                                         O O O                                                                                        ##STR133##                                100                                                                                ##STR134##   CH.sub.3                                                                         O O O                                                                                        ##STR135##                                101                                                                                ##STR136##   CH.sub.3                                                                         O O O                                                                                        ##STR137##       165-170                  102                                                                                ##STR138##   CH.sub.3                                                                         O O O                                                                                        ##STR139##                                103                                                                                ##STR140##   CH.sub.3                                                                         O O O                                                                                        ##STR141##                                104                                                                                ##STR142##   CH.sub.3                                                                         O O O                                                                                        ##STR143##       166-169                  105                                                                                ##STR144##   CH.sub.3                                                                         O O O                                                                                        ##STR145##                                106                                                                                ##STR146##   CH.sub.3                                                                         O O O                                                                                        ##STR147##                                107                                                                                ##STR148##   CH.sub.3                                                                         O O O                                                                                        ##STR149##       142-146                  108                                                                                ##STR150##   CH.sub.3                                                                         O O O                                                                                        ##STR151##       158-162                  109                                                                                ##STR152##   CH.sub.3                                                                         O O O                                                                                        ##STR153##       128-133                  110                                                                                ##STR154##   CH.sub.3                                                                         O O O                                                                                        ##STR155##                                111                                                                                ##STR156##   CH.sub.3                                                                         O O O                                                                                        ##STR157##                                112                                                                                ##STR158##   CH.sub.3                                                                         O O O                                                                                        ##STR159##       137-142                  113                                                                                ##STR160##   CH.sub.3                                                                         O O O                                                                                        ##STR161##                                114                                                                                ##STR162##   CH.sub.3                                                                         O O O                                                                                        ##STR163##       151-155                  115                                                                                ##STR164##   CH.sub.3                                                                         O O O                                                                                        ##STR165##       144-147                  116                                                                                ##STR166##   CH.sub.3                                                                         O O O                                                                                        ##STR167##       145-147                  117                                                                                ##STR168##   CH.sub.3                                                                         O O O                                                                                        ##STR169##       166-170                  118                                                                                ##STR170##   CH.sub.3                                                                         O O O                                                                                        ##STR171##                                119                                                                                ##STR172##   CH.sub.3                                                                         O O O                                                                                        ##STR173##                                120                                                                                ##STR174##   CH.sub.3                                                                         O O O                                                                                        ##STR175##                                121                                                                                ##STR176##   CH.sub.3                                                                         O O O                                                                                        ##STR177##                                122                                                                                ##STR178##   CH.sub.3                                                                         O O O                                                                                        ##STR179##                                123                                                                                ##STR180##   CH.sub.3                                                                         O O O                                                                                        ##STR181##                                124                                                                                ##STR182##   CH.sub.3                                                                         O O O                                                                                        ##STR183##       137-142                  125                                                                                ##STR184##   CH.sub.3                                                                         O O O                                                                                        ##STR185##                                126                                                                                ##STR186##   CH.sub.3                                                                         O O O                                                                                        ##STR187##                                127                                                                                ##STR188##   CH.sub.3                                                                         O O O                                                                                        ##STR189##                                128                                                                                ##STR190##   CH.sub.3                                                                         O O O                                                                                        ##STR191##                                129                                                                                ##STR192##   CH.sub.3                                                                         O O O                                                                                        ##STR193##       114-117                  130                                                                                ##STR194##   CH.sub.3                                                                         O O O                                                                                        ##STR195##                                131                                                                                ##STR196##   CH.sub.3                                                                         O O O                                                                                        ##STR197##                                132                                                                                ##STR198##   CH.sub.3                                                                         O O O                                                                                        ##STR199##                                133                                                                                ##STR200##   CH.sub.3                                                                         O O O                                                                                        ##STR201##                                134                                                                                ##STR202##   CH.sub.3                                                                         O O O                                                                                        ##STR203##       133-138                  135                                                                                ##STR204##   CH.sub.3                                                                         O O O                                                                                        ##STR205##       156-160                  136                                                                                ##STR206##   CH.sub.3                                                                         O O O                                                                                        ##STR207##                                137                                                                                ##STR208##   CH.sub.3                                                                         O O O                                                                                        ##STR209##                                138                                                                                ##STR210##   CH.sub.3                                                                         O O O                                                                                        ##STR211##                                139                                                                                ##STR212##   CH.sub.3                                                                         O O O                                                                                        ##STR213##                                140                                                                                ##STR214##   CH.sub.3                                                                         O O O                                                                                        ##STR215##                                141                                                                                ##STR216##   CH.sub.3                                                                         O O O                                                                                        ##STR217##                                142                                                                                ##STR218##   CH.sub.3                                                                         O O O                                                                                        ##STR219##                                143                                                                                ##STR220##   CH.sub.3                                                                         O O O                                                                                        ##STR221##                                144                                                                                ##STR222##   CH.sub.3                                                                         O O O                                                                                        ##STR223##                                145                                                                                ##STR224##   CH.sub.3                                                                         O O O                                                                                        ##STR225##                                146                                                                                ##STR226##   CH.sub.3                                                                         O O O                                                                                        ##STR227##                                147                                                                                ##STR228##   CH.sub.3                                                                         O O O                                                                                        ##STR229##                                148                                                                                ##STR230##   CH.sub.3                                                                         O O O                                                                                        ##STR231##                                149                                                                                ##STR232##   CH.sub.3                                                                         O O O                                                                                        ##STR233##                                150                                                                                ##STR234##   CH.sub.3                                                                         O O O                                                                                        ##STR235##                                151                                                                                ##STR236##   CH.sub.3                                                                         O O O                                                                                        ##STR237##                                152                                                                                ##STR238##   CH.sub.3                                                                         O O O                                                                                        ##STR239##                                153                                                                                ##STR240##   CH.sub.3                                                                         O O O                                                                                        ##STR241##                                154                                                                                ##STR242##   CH.sub.3                                                                         O O O                                                                                        ##STR243##       146-150                  155                                                                                ##STR244##   CH.sub.3                                                                         O O O                                                                                        ##STR245##                                156                                                                                ##STR246##   CH.sub.3                                                                         O O O                                                                                        ##STR247##                                157                                                                                ##STR248##   CH.sub.3                                                                         O O O                                                                                        ##STR249##        97-100                  158                                                                                ##STR250##   CH.sub.3                                                                         O O O                                                                                        ##STR251##                                159                                                                                ##STR252##   CH.sub.3                                                                         O O O                                                                                        ##STR253##                                160                                                                                ##STR254##   CH.sub.3                                                                         O O O                                                                                        ##STR255##       152-155                  161                                                                                ##STR256##   CH.sub.3                                                                         O O O                                                                                        ##STR257##                                162                                                                                ##STR258##   CH.sub.3                                                                         O O O                                                                                        ##STR259##                                163                                                                                ##STR260##   CH.sub.3                                                                         O O O                                                                                        ##STR261##       137-140                  164                                                                                ##STR262##   CH.sub.3                                                                         O O O                                                                                        ##STR263##                                165                                                                                ##STR264##   CH.sub.3                                                                         O O O                                                                                        ##STR265##                                166                                                                                ##STR266##   CH.sub.3                                                                         O O O                                                                                        ##STR267##       134-137                  167                                                                                ##STR268##   CH.sub.3                                                                         O O O                                                                                        ##STR269##                                168                                                                                ##STR270##   CH.sub.3                                                                         O O O                                                                                        ##STR271##                                169                                                                                ##STR272##   CH.sub.3                                                                         O O O                                                                                        ##STR273##       139-145                  170                                                                                ##STR274##   CH.sub.3                                                                         O O O                                                                                        ##STR275##                                171                                                                                ##STR276##   CH.sub.3                                                                         O O O                                                                                        ##STR277##                                172                                                                                ##STR278##   CH.sub.3                                                                         O O O                                                                                        ##STR279##                                173                                                                                ##STR280##   CH.sub.3                                                                         O O O                                                                                        ##STR281##                                174                                                                                ##STR282##   CH.sub.3                                                                         O O O                                                                                        ##STR283##                                175                                                                                ##STR284##   CH.sub.3                                                                         O O O                                                                                        ##STR285##                                176                                                                                ##STR286##   CH.sub.3                                                                         O O O                                                                                        ##STR287##                                177                                                                                ##STR288##   CH.sub.3                                                                         O O O                                                                                        ##STR289##                                178                                                                                ##STR290##   CH.sub.3                                                                         O O O                                                                                        ##STR291##                                179                                                                                ##STR292##   CH.sub.3                                                                         O O O                                                                                        ##STR293##                                180                                                                                ##STR294##   CH.sub.3                                                                         O O O                                                                                        ##STR295##                                181                                                                                ##STR296##   CH.sub.3                                                                         O O O                                                                                        ##STR297##                                182                                                                                ##STR298##   CH.sub.3                                                                         O O O                                                                                        ##STR299##                                183                                                                                ##STR300##   CH.sub.3                                                                         O O O                                                                                        ##STR301##                                184 CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.3                                                                         O O O                                                                                        ##STR302##       170-175                  185 CH.sub.2 Cl   CH.sub.3                                                                         O O O                                                                                        ##STR303##                                186 CH(Cl)CH.sub.3                                                                              CH.sub.3                                                                         O O O                                                                                        ##STR304##                                187 CH.sub.2 CF.sub.3                                                                           CH.sub.3                                                                         O O O                                                                                        ##STR305##                                188                                                                                ##STR306##   CH.sub.3                                                                         O O O                                                                                        ##STR307##                                189 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3                                                                         O O O                                                                                        ##STR308##                                190 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3                                                                         O O O                                                                                        ##STR309##                                191 CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3                                                                         O O O                                                                                        ##STR310##                                192                                                                                ##STR311##   CH.sub.3                                                                         O O O                                                                                        ##STR312##                                193                                                                                ##STR313##   CH.sub.3                                                                         O O O                                                                                        ##STR314##       125-128                  194                                                                                ##STR315##   CH.sub.3                                                                         O O O                                                                                        ##STR316##                                195                                                                                ##STR317##   CH.sub.3                                                                         O O O                                                                                        ##STR318##        98-101                  196                                                                                ##STR319##   CH.sub.3                                                                         O O O                                                                                        ##STR320##                                197 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR321##                                198 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR322##                                199 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR323##                                200 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR324##                                201                                                                                ##STR325##   CH.sub.3                                                                         O O O                                                                                        ##STR326##                                202                                                                                ##STR327##   CH.sub.3                                                                         O O O                                                                                        ##STR328##                                203                                                                                ##STR329##   CH.sub.3                                                                         S O O                                                                                        ##STR330##       111-113                  204                                                                                ##STR331##   CH.sub.3                                                                         S O O                                                                                        ##STR332##       149-152                  205                                                                                ##STR333##   CH.sub.3                                                                         S O O                                                                                        ##STR334##       146-149                  206                                                                                ##STR335##   CH.sub.3                                                                         O S O                                                                                        ##STR336##                                207                                                                                ##STR337##   CH.sub.3                                                                         O S O                                                                                        ##STR338##                                208                                                                                ##STR339##   CH.sub.3                                                                         O S O                                                                                        ##STR340##       not determined           209                                                                                ##STR341##   CH.sub.3                                                                         S S O                                                                                        ##STR342##                                210                                                                                ##STR343##   CH.sub.3                                                                         S S O                                                                                        ##STR344##                                211                                                                                ##STR345##   CH.sub.3                                                                         S S O                                                                                        ##STR346##       not determined           212                                                                                ##STR347##   CH.sub.3                                                                         O O S                                                                                        ##STR348##       140-144                  213                                                                                ##STR349##   CH.sub.3                                                                         O O S                                                                                        ##STR350##       136-140                  214                                                                                ##STR351##   CH.sub.3                                                                         O O S                                                                                        ##STR352##       123-126                  215                                                                                ##STR353##   CH.sub.3                                                                         O O S                                                                                        ##STR354##       144-146                  216 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR355##       74-78                    217 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR356##       109-112                  218 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR357##                                219 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR358##       122-126                  220 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR359##       165-169                  221 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR360##       158-160                  222 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O NCH.sub.3                                                                                ##STR361##                                223                                                                                ##STR362##   CH.sub.3                                                                         O O NCOCH.sub.3                                                                              ##STR363##                                224                                                                                ##STR364##   CH.sub.3                                                                         O O                                                                                ##STR365##                                                                              ##STR366##                                225                                                                                ##STR367##   CH.sub.3                                                                         O O NCO.sub.2 CH.sub.3                                                                       ##STR368##                                226 C.sub.4 H.sub.9 -t                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR369##       101-104                  227 C.sub.4 H.sub.9 -t                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR370##       128-130                  228 C.sub.4 H.sub.9 -t                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR371##       100-106                  229 C.sub.4 H.sub.9 -t                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR372##                                230                                                                                ##STR373##   C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR374##       149-154                  231                                                                                ##STR375##   C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR376##       152-154                  232                                                                                ##STR377##   C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR378##       108-112                  233 C.sub.4 H.sub.9 -t                                                                          H  O O O                                                                                        ##STR379##       1.5081                   234 C.sub.4 H.sub.9 -t                                                                          H  O O O                                                                                        ##STR380##                                235 C.sub.4 H.sub.9 -t                                                                          H  O O O                                                                                        ##STR381##       not determined           236                                                                                ##STR382##   H  O O O                                                                                        ##STR383##       125-130                  237                                                                                ##STR384##   H  O O O                                                                                        ##STR385##                                238                                                                                ##STR386##   H  O O O                                                                                        ##STR387##       43-46                    239 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR388##                                240 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR389##                                241 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR390##                                242 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR391##                                243 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR392##                                244 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR393##                                245 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR394##                                246 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR395##       104-109                  247 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR396##                                248 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR397##                                249                                                                                ##STR398##   CH.sub.3                                                                         O O O                                                                                        ##STR399##                                250                                                                                ##STR400##   CH.sub.3                                                                         O O O                                                                                        ##STR401##                                251                                                                                ##STR402##   CH.sub.3                                                                         O O O                                                                                        ##STR403##                                252                                                                                ##STR404##   CH.sub.3                                                                         O O O                                                                                        ##STR405##                                253                                                                                ##STR406##   CH.sub.3                                                                         O O O                                                                                        ##STR407##                                254 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR408##                                255 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR409##                                256                                                                                ##STR410##   CH.sub.3                                                                         O O O                                                                                        ##STR411##                                257 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR412##                                258 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR413##                                259                                                                                ##STR414##   CH.sub.3                                                                         O O O                                                                                        ##STR415##                                260 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR416##                                261 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR417##                                262 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR418##                                263 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR419##                                264                                                                                ##STR420##   CH.sub.3                                                                         O O NH                                                                                       ##STR421##                                265                                                                                ##STR422##   CH.sub.3                                                                         O O NH                                                                                       ##STR423##                                266 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR424##                                267 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR425##                                268 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR426##                                269 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR427##                                270 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR428##                                271                                                                                ##STR429##   CH.sub.3                                                                         O O O                                                                                        ##STR430##                                272                                                                                ##STR431##   CH.sub.3                                                                         O O O                                                                                        ##STR432##                                273                                                                                ##STR433##   CH.sub.3                                                                         O O O                                                                                        ##STR434##                                274                                                                                ##STR435##   CH.sub.3                                                                         O O O                                                                                        ##STR436##                                275                                                                                ##STR437##   CH.sub.3                                                                         O O O                                                                                        ##STR438##       60-65                    276 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR439##                                277 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR440##                                278                                                                                ##STR441##   CH.sub.3                                                                         O O O                                                                                        ##STR442##                                279 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR443##                                280 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR444##                                281 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR445##                                282 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR446##                                283                                                                                ##STR447##   CH.sub.3                                                                         O O O                                                                                        ##STR448##                                284                                                                                ##STR449##   CH.sub.3                                                                         O O O                                                                                        ##STR450##                                285 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR451##                                286 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR452##                                287                                                                                ##STR453##   CH.sub.3                                                                         O O O                                                                                        ##STR454##                                288                                                                                ##STR455##   CH.sub.3                                                                         O O S                                                                                        ##STR456##                                289                                                                                ##STR457##   CH.sub.3                                                                         O O NH                                                                                       ##STR458##                                290 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR459##                                291 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR460##                                292                                                                                ##STR461##   CH.sub.3                                                                         O O NH                                                                                       ##STR462##                                293                                                                                ##STR463##   CH.sub.3                                                                         O O NH                                                                                       ##STR464##                                294 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR465##                                295 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR466##                                296 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR467##                                297 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR468##                                298                                                                                ##STR469##   CH.sub.3                                                                         O O O                                                                                        ##STR470##                                299                                                                                ##STR471##   CH.sub.3                                                                         O O O                                                                                        ##STR472##                                300                                                                                ##STR473##   CH.sub.3                                                                         O O O                                                                                        ##STR474##                                301                                                                                ##STR475##   CH.sub.3                                                                         O O NH                                                                                       ##STR476##                                302                                                                                ##STR477##   CH.sub.3                                                                         O O NH                                                                                       ##STR478##                                303                                                                                ##STR479##   CH.sub.3                                                                         O O NH                                                                                       ##STR480##                                304 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR481##                                305 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR482##                                306 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR483##                                307 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR484##                                308 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR485##                                309 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR486##                                310 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR487##                                311                                                                                ##STR488##   CH.sub.3                                                                         O O NCH.sub.2 OCH.sub.3                                                                      ##STR489##                                312                                                                                ##STR490##   CH.sub.3                                                                         O O SO                                                                                       ##STR491##                                313                                                                                ##STR492##   CH.sub.3                                                                         O O SO.sub.2                                                                                 ##STR493##                                314                                                                                ##STR494##   CH.sub.3                                                                         O O NH                                                                                       ##STR495##                                315 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR496##                                316 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR497##                                317                                                                                ##STR498##   CH.sub.3                                                                         O O O                                                                                        ##STR499##                                318                                                                                ##STR500##   CH.sub.3                                                                         O O O                                                                                        ##STR501##                                319                                                                                ##STR502##   CH.sub.3                                                                         O O O                                                                                        ##STR503##                                320                                                                                ##STR504##   CH.sub.3                                                                         O O O                                                                                        ##STR505##                                321                                                                                ##STR506##   CH.sub.3                                                                         O O O                                                                                        ##STR507##                                322                                                                                ##STR508##   CH.sub.3                                                                         O O O                                                                                        ##STR509##                                323                                                                                ##STR510##   CH.sub.3                                                                         O O O                                                                                        ##STR511##       115-117                  324                                                                                ##STR512##   CH.sub.3                                                                         O O O                                                                                        ##STR513##                                325                                                                                ##STR514##   CH.sub.3                                                                         O O O                                                                                        ##STR515##                                326                                                                                ##STR516##   CH.sub.3                                                                         O O O                                                                                        ##STR517##       127-129                  327 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR518##       93-96                    328 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR519##       48-51                    329 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR520##       122-125                  330 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR521##       74-77                    331 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR522##       1.5164                   332 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR523##       1.5319                   333 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR524##       1.5361                   334 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR525##       102-104                  335 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR526##       80-84                    336 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR527##       133-137                  337 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR528##       1.5360                   338 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR529##       1.5361                   339 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR530##       1.5274                   340 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR531##       1.5245                   341 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR532##       1.5269                   342 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR533##       66-69                    343 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR534##       71-74                    344 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR535##       1.5312                   345 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR536##       161-163                  346 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR537##       167-171                  347 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR538##       166-172                  348 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR539##       121-123                  349 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR540##       125-129                  350 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR541##       103-106                  351 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR542##       122-125                  352 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR543##       155-158                  353 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR544##       130-134                  354 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O SO                                                                                       ##STR545##       119-123                  355 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O SO.sub.2                                                                                 ##STR546##       151-153                  356 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR547##       177-180                  357 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR548##       137-140                  358 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NCH.sub.3                                                                                ##STR549##       145-148                  359 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR550##       155-156                  360 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NCH.sub.3                                                                                ##STR551##       141-143                  361 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR552##       85-90                    362 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR553##       143-145                  363 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NCH.sub.3                                                                                ##STR554##       65-67                    364 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR555##       146-149                  365 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR556##       115-118                  366 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR557##       124-127                  367 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR558##       119-121                  368 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR559##       107-110                  369 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR560##       111-115                  370 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O S                                                                                        ##STR561##       109-112                  371 C.sub.4 H.sub.9 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR562##       125-130                  372 C.sub.5 H.sub.11                                                                            CH.sub.3                                                                         O O O                                                                                        ##STR563##       109-111                  373 C.sub.6 H.sub.13                                                                            CH.sub.3                                                                         O O O                                                                                        ##STR564##       107-110                  374                                                                                ##STR565##   CH.sub.3                                                                         O O O                                                                                        ##STR566##       122-125                  375 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NCOCH.sub.3                                                                              ##STR567##       56-60                    376                                                                                ##STR568##   CH.sub.3                                                                         O O O                                                                                        ##STR569##       181-184                  377                                                                                ##STR570##   CH.sub.3                                                                         O O O                                                                                        ##STR571##       201-204                  378                                                                                ##STR572##   CH.sub.3                                                                         O O O                                                                                        ##STR573##       111-116                  379                                                                                ##STR574##   CH.sub.3                                                                         O O O                                                                                        ##STR575##       141-142                  380                                                                                ##STR576##   CH.sub.3                                                                         O O O                                                                                        ##STR577##       133-136                  381                                                                                ##STR578##   CH.sub.3                                                                         O O O                                                                                        ##STR579##       148-151                  382                                                                                ##STR580##   CH.sub.3                                                                         O O O                                                                                        ##STR581##       161-164                  383                                                                                ##STR582##   CH.sub.3                                                                         O O O                                                                                        ##STR583##       102-107                  384                                                                                ##STR584##   CH.sub.3                                                                         O O O                                                                                        ##STR585##       159-162                  385                                                                                ##STR586##   CH.sub.3                                                                         O O NH                                                                                       ##STR587##       130-134                  386                                                                                ##STR588##   CH.sub.3                                                                         O O S                                                                                        ##STR589##       127-130                  387                                                                                ##STR590##   CH.sub.3                                                                         O O S                                                                                        ##STR591##       108-110                  388                                                                                ##STR592##   CH.sub.3                                                                         O O NH                                                                                       ##STR593##       154-156                  389                                                                                ##STR594##   CH.sub.3                                                                         O O NCH.sub.3                                                                                ##STR595##       125-130                  390                                                                                ##STR596##   CH.sub.3                                                                         O O NH                                                                                       ##STR597##       147-149                  391                                                                                ##STR598##   CH.sub.3                                                                         O O NCH.sub.3                                                                                ##STR599##       64-70                    392                                                                                ##STR600##   CH.sub.3                                                                         O O NH                                                                                       ##STR601##       117-119                  393                                                                                ##STR602##   CH.sub.3                                                                         O O NH                                                                                       ##STR603##       156-160                  394                                                                                ##STR604##   CH.sub.3                                                                         O O O                                                                                        ##STR605##       156-162                  395                                                                                ##STR606##   CH.sub.3                                                                         O O O                                                                                        ##STR607##       137-140                  396                                                                                ##STR608##   CH.sub.3                                                                         O O O                                                                                        ##STR609##       174-179                  397                                                                                ##STR610##   CH.sub.3                                                                         O O O                                                                                        ##STR611##       153-156                  398                                                                                ##STR612##   CH.sub.3                                                                         O O O                                                                                        ##STR613##       130-134                  399                                                                                ##STR614##   CH.sub.3                                                                         O O O                                                                                        ##STR615##       156-161                  400                                                                                ##STR616##   CH.sub.3                                                                         O O O                                                                                        ##STR617##       125-129                  401                                                                                ##STR618##   CH.sub.3                                                                         O O O                                                                                        ##STR619##       155-158                  402                                                                                ##STR620##   CH.sub.3                                                                         O O O                                                                                        ##STR621##       141-144                  403                                                                                ##STR622##   CH.sub.3                                                                         O O O                                                                                        ##STR623##       153-154                  404                                                                                ##STR624##   CH.sub.3                                                                         O O O                                                                                        ##STR625##       144-148                  405                                                                                ##STR626##   CH.sub.3                                                                         O O O                                                                                        ##STR627##       129-133                  406                                                                                ##STR628##   CH.sub.3                                                                         O O NH                                                                                       ##STR629##       60-62                    407 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR630##       90-93                    408                                                                                ##STR631##   CH.sub.3                                                                         O O O                                                                                        ##STR632##       129-130                  409 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR633##       111-112                  410 C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR634##       129-131                  411                                                                                ##STR635##   CH.sub.3                                                                         O O O                                                                                        ##STR636##       163-164                  412 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR637##       118-120                  413                                                                                ##STR638##   CH.sub.3                                                                         O O O                                                                                        ##STR639##       123-124                  414 C.sub.4 H.sub.9 -t                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR640##       122-125                  415 C.sub.4 H.sub.9 -t                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR641##       135-137                  416 C.sub.3 H.sub.7 -i                                                                          C.sub.2 H.sub.5                                                                  O O S                                                                                        ##STR642##       85-86                    417 C.sub.3 H.sub.7 -i                                                                          C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR643##       145-148                  418                                                                                ##STR644##   C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR645##       139-141                  419                                                                                ##STR646##   C.sub.2 H.sub.5                                                                  O O S                                                                                        ##STR647##       105-107                  420                                                                                ##STR648##   C.sub.2 H.sub.5                                                                  O O S                                                                                        ##STR649##       130-133                  421                                                                                ##STR650##   C.sub.2 H.sub.5                                                                  O O NH                                                                                       ##STR651##       137-139                  422                                                                                ##STR652##   C.sub.2 H.sub.5                                                                  O O NCH.sub.3                                                                                ##STR653##       53-56                    423                                                                                ##STR654##   C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR655##       159-163                  424                                                                                ##STR656##   C.sub.2 H.sub.5                                                                  O O O                                                                                        ##STR657##       150-153                  425 C.sub.3 H.sub.7 -i                                                                          H  O O O                                                                                        ##STR658##       118-121                  426                                                                                ##STR659##   H  O O O                                                                                        ##STR660##       127-132                  427                                                                                ##STR661##   H  O O O                                                                                        ##STR662##       141-145                  428 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                        ##STR663##       217-220                  429                                                                                ##STR664##   CH.sub.3                                                                         O O O                                                                                        ##STR665##       65-68                    430 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         S O O                                                                                        ##STR666##       161-163                  431 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         S O O                                                                                        ##STR667##       152-154                  432 C.sub.2 H.sub.5                                                                             CH.sub.3                                                                         S O O                                                                                        ##STR668##       164-166                  433                                                                                ##STR669##   CH.sub.3                                                                         O O O                                                                                        ##STR670##       118-120                  434                                                                                ##STR671##   CH.sub.3                                                                         O O NCOCH.sub.3                                                                              ##STR672##                                435 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NCO.sub.2 CH.sub.3                                                                       ##STR673##                                436 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O                                                                                ##STR674##                                                                              ##STR675##       71-73                    437 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NCH.sub.2 OCH.sub.3                                                                      ##STR676##                                438                                                                                ##STR677##   CH.sub.3                                                                         O O O                                                                                        ##STR678##                                439                                                                                ##STR679##   CH.sub.3                                                                         O O O                                                                                        ##STR680##       135-138                  440                                                                                ##STR681##   CH.sub.3                                                                         O O O                                                                                        ##STR682##       112-114                  441 C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O NH                                                                                       ##STR683##                                __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR684##                                                                                                             Melting Point (°C.) or       Compound No.                                                                          R.sup.1       R.sup.9                                                                          Z.sup.1                                                                         Z.sup.2                                                                         Z.sup.3                                                                         A          Reflactive Index                                                              (n.sub.D.sup.20)                    __________________________________________________________________________    442                                                                                    ##STR685##   CH.sub.3                                                                         O O O                                                                                ##STR686##                                    443     C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                ##STR687##                                    444     C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                ##STR688##                                    445                                                                                    ##STR689##   CH.sub.3                                                                         O O O                                                                                ##STR690##                                    446                                                                                    ##STR691##   CH.sub.3                                                                         O O O                                                                                ##STR692##                                    447     C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                ##STR693##                                    448                                                                                    ##STR694##   CH.sub.3                                                                         O O O                                                                                ##STR695##                                    449     C.sub.4 H.sub.9 -t                                                                          CH.sub.3                                                                         O O O                                                                                ##STR696##                                    450     C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                         O O O                                                                                ##STR697##                                    __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR698##                                                                                                      Melting Point                              Com-                               (°C.) or                            pound                              Reflactive                                 No. R.sup.1     R.sup.2  Q         Index (n.sub.D .sup.20)                    __________________________________________________________________________    451                                                                                ##STR699## C.sub.3 H.sub.7                                                                         ##STR700##                                                                             117-119                                    452 C.sub.4 H.sub.9 -t                                                                        C.sub.3 H.sub.7                                                                         ##STR701##                                                                             78-80                                      453 C.sub.4 H.sub.9 -t                                                                        C.sub.3 H.sub.7                                                                         ##STR702##                                                                             105-107                                    454 C.sub.4 H.sub.9 -t                                                                        C.sub.3 H.sub.7                                                                         ##STR703##                                                                             93-95                                      455 C.sub.4 H.sub.9 -t                                                                        C.sub.4 H.sub.9 -i                                                                      ##STR704##                                                                             not determined                             456 C.sub.4 H.sub.9 -t                                                                         ##STR705##                                                                             ##STR706##                                                                             140-142                                    457 C.sub.4 H.sub.9 -t                                                                        C.sub.4 H.sub.9 -t                                                                      ##STR707##                                                                             68-71                                      458 C.sub.4 H.sub.9 -t                                                                         ##STR708##                                                                             ##STR709##                                                                             61-64                                      459 C.sub.4 H.sub.9 -t                                                                         ##STR710##                                                                             ##STR711##                                                                             124-126                                    460 C.sub.4 H.sub.9 -t                                                                         ##STR712##                                                                             ##STR713##                                                                             1.5132                                     461 C.sub.4 H.sub.9 -t                                                                         ##STR714##                                                                             ##STR715##                                                                             107-109                                    462 C.sub.3 H.sub.7 -i                                                                         ##STR716##                                                                             ##STR717##                                                                             155-158                                    463 C.sub.3 H.sub.7 -i                                                                         ##STR718##                                                                             ##STR719##                                                                             149-151                                    464 C.sub.3 H.sub.7 -i                                                                         ##STR720##                                                                             ##STR721##                                                                             158-161                                    465                                                                                ##STR722## C.sub.3 H.sub.7                                                                         ##STR723##                                                                             88-91                                      466                                                                                ##STR724## C.sub.4 H.sub.9 -i                                                                      ##STR725##                                                                             43-47                                      467                                                                                ##STR726##                                                                                ##STR727##                                                                             ##STR728##                                                                             153-156                                    468                                                                                ##STR729## C.sub.4 H.sub.9 -t                                                                      ##STR730##                                                                             75-78                                      469                                                                                ##STR731##                                                                                ##STR732##                                                                             ##STR733##                                                                             68-71                                      470                                                                                ##STR734##                                                                                ##STR735##                                                                             ##STR736##                                                                             152-155                                    471                                                                                ##STR737##                                                                                ##STR738##                                                                             ##STR739##                                                                             141-145                                    472                                                                                ##STR740##                                                                                ##STR741##                                                                             ##STR742##                                                                             170-174                                    473                                                                                ##STR743## C.sub.4 H.sub.9 -t                                                                      ##STR744##                                                                             46-49                                      474                                                                                ##STR745##                                                                                ##STR746##                                                                             ##STR747##                                                                             155-157                                    475                                                                                ##STR748##                                                                                ##STR749##                                                                             ##STR750##                                                                             128-129                                    476                                                                                ##STR751## C.sub.3 H.sub.7 -i                                                                      ##STR752##                                                                             127-129                                    477                                                                                ##STR753## C.sub.3 H.sub.7 -i                                                                      ##STR754##                                                                             152-154                                    478 C.sub.4 H.sub.9 -t                                                                        C.sub.3 H.sub.7 -i                                                                      ##STR755##                                                                             100-103                                    479 C.sub.4 H.sub.9 -t                                                                        C.sub.3 H.sub.7 -i                                                                      ##STR756##                                                                             105-106                                    480 C.sub.4 H.sub.9 -t                                                                        C.sub.3 H.sub.7 -i                                                                      ##STR757##                                                                             109-112                                    481 C.sub.3 H.sub.7 -i                                                                        C.sub.3 H.sub.7 -i                                                                      ##STR758##                                                                             173-175                                    482                                                                                ##STR759## C.sub.3 H.sub.7 -i                                                                      ##STR760##                                                                             128-129                                    __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR761##                                                                                                            Melting Point (°C.) or        Compound No.                                                                          R.sup.1  R.sup.2                                                                           R.sup.4                                                                          Z.sup.3                                                                           A            Reflactive Index                     __________________________________________________________________________                                             (n.sub.D.sup.20)                     483     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 i                                                                 CH.sub.3                                                                          ##STR762##                                                                        ##STR763##  82-87                                484     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR764##                                                                        ##STR765##  156-159                              485     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR766##                                                                        ##STR767##  145-149                              486     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR768##                                                                        ##STR769##   96-100                              487     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR770##                                                                        ##STR771##  157-158                              488     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR772##                                                                        ##STR773##  83-86                                489     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR774##                                                                        ##STR775##  144-146                              490     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR776##                                                                        ##STR777##  70-73                                491     C.sub.4 H.sub.9 -t                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR778##                                                                        ##STR779##  140--143                             492     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR780##                                                                        ##STR781##  179-182                              493     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR782##                                                                        ##STR783##  251-255                              494     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR784##                                                                        ##STR785##  219--222                             495     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR786##                                                                        ##STR787##  88-92                                496     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR788##                                                                        ##STR789##  211-212                              497     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR790##                                                                        ##STR791##  210-213                              498     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR792##                                                                        ##STR793##  200-203                              499     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR794##                                                                        ##STR795##  68-72                                500     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR796##                                                                        ##STR797##  205-210                              501     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR798##                                                                        ##STR799##  113-115                              502     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR800##                                                                        ##STR801##  184-186                              503     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR802##                                                                        ##STR803##  73-75                                504     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                         COO                                                                                ##STR804##  184-185                              505     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                         COO                                                                                ##STR805##  151-153                              506     C.sub.3 H.sub.7 -i                                                                     C.sub.4 H.sub.9 -i                                                                CH.sub.3                                                                          ##STR806##                                                                        ##STR807##  197-198                              507     C.sub.3 H.sub.7 -i                                                                     C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          ##STR808##                                                                        ##STR809##  84-87                                508     C.sub.4 H.sub.9 -s                                                                     C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR810##                                                                        ##STR811##  165-167                              509                                                                                    ##STR812##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR813##                                                                        ##STR814##  197-199                              510                                                                                    ##STR815##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR816##                                                                        ##STR817##  201-204                              511                                                                                    ##STR818##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR819##                                                                        ##STR820##  219-221                              512                                                                                    ##STR821##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR822##                                                                        ##STR823##  245-250                              513                                                                                    ##STR824##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR825##                                                                        ##STR826##  225-230                              514                                                                                    ##STR827##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR828##                                                                        ##STR829##  199-202                              515                                                                                    ##STR830##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR831##                                                                        ##STR832##  194-197                              516                                                                                    ##STR833##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR834##                                                                        ##STR835##  173-175                              517                                                                                    ##STR836##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR837##                                                                        ##STR838##  69-71                                518                                                                                    ##STR839##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR840##                                                                        ##STR841##  149-153                              519                                                                                    ##STR842##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR843##                                                                        ##STR844##  158-161                              520                                                                                    ##STR845##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR846##                                                                        ##STR847##  202-203                              521                                                                                    ##STR848##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                         COO                                                                                ##STR849##  168-170                              522                                                                                    ##STR850##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                         COO                                                                                ##STR851##  175-178                              523                                                                                    ##STR852##                                                                            C.sub.4 H.sub.9 -s                                                                CH.sub.3                                                                          ##STR853##                                                                        ##STR854##  157-159                              524                                                                                    ##STR855##                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          ##STR856##                                                                        ##STR857##  156-158                              525                                                                                    ##STR858##                                                                            C.sub.3 H.sub.7 -i                                                                CH.sub.3                                                                          ##STR859##                                                                        ##STR860##  182-184                              526     C.sub.3 H.sub.7 -i                                                                     C.sub.3 H.sub.7 -i                                                                H                                                                                 ##STR861##                                                                        ##STR862##  181-185                          

    TABLE 5                                                                       __________________________________________________________________________     ##STR863##                                                                                                                     Melting Point                                                                 (°C.) or             Compound No.                                                                           R.sup.1       Z.sup.1                                                                          Z.sup.2                                                                         Z.sup.3                                                                            A                Reflactive Index                                                              (n.sub.D.sup.20)            __________________________________________________________________________    527      C.sub.4 H.sub.9 -t                                                                          O  O O                                                                                   ##STR864##      158-160                     528      C.sub.4 H.sub.9 -t                                                                          O  O O                                                                                   ##STR865##                                  529      C.sub.4 H.sub.9 -t                                                                          O  O O                                                                                   ##STR866##                                  530      C.sub.4 H.sub.9 -t                                                                          O  O O                                                                                   ##STR867##                                  531      C.sub.4 H.sub.9 -t                                                                          O  O O                                                                                   ##STR868##                                  532      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR869##                                  533      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR870##                                  534      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR871##                                  535                                                                                     ##STR872##   O  O O                                                                                   ##STR873##                                  536                                                                                     ##STR874##   O  O O                                                                                   ##STR875##                                  537                                                                                     ##STR876##   O  O O                                                                                   ##STR877##                                  538                                                                                     ##STR878##   O  O O                                                                                   ##STR879##                                  539                                                                                     ##STR880##   O  O O                                                                                   ##STR881##                                  540                                                                                     ##STR882##   O  O O                                                                                   ##STR883##                                  541                                                                                     ##STR884##   O  O O                                                                                   ##STR885##                                  542                                                                                     ##STR886##   O  O O                                                                                   ##STR887##                                  543                                                                                     ##STR888##   O  O O                                                                                   ##STR889##                                  544                                                                                     ##STR890##   S  O O                                                                                   ##STR891##                                  545                                                                                     ##STR892##   O  S O                                                                                   ##STR893##                                  546                                                                                     ##STR894##   S  S O                                                                                   ##STR895##                                  547                                                                                     ##STR896##   O  O S                                                                                   ##STR897##                                  548                                                                                     ##STR898##   O  O S                                                                                   ##STR899##                                  549                                                                                     ##STR900##   O  O S                                                                                   ##STR901##                                  550                                                                                     ##STR902##   O  O S                                                                                   ##STR903##                                  551      C.sub.4 H.sub.9 -t                                                                          O  O S                                                                                   ##STR904##      75-77                       552      C.sub.4 H.sub.9 -t                                                                          O  O S                                                                                   ##STR905##                                  553      C.sub.4 H.sub.9 -t                                                                          O  O S                                                                                   ##STR906##                                  554                                                                                     ##STR907##   O  O O                                                                                   ##STR908##                                  555                                                                                     ##STR909##   O  O O                                                                                   ##STR910##                                  556                                                                                     ##STR911##   O  O O                                                                                   ##STR912##                                  557                                                                                     ##STR913##   O  O O                                                                                   ##STR914##                                  558                                                                                     ##STR915##   O  O O                                                                                   ##STR916##                                  559                                                                                     ##STR917##   O  O O                                                                                   ##STR918##                                  560                                                                                     ##STR919##   O  O O                                                                                   ##STR920##                                  561                                                                                     ##STR921##   O  O O                                                                                   ##STR922##                                  562                                                                                     ##STR923##   O  O O                                                                                   ##STR924##                                  563                                                                                     ##STR925##   O  O O                                                                                   ##STR926##                                  564                                                                                     ##STR927##   O  O O                                                                                   ##STR928##                                  565                                                                                     ##STR929##   O  O O                                                                                   ##STR930##                                  566                                                                                     ##STR931##   O  O O                                                                                   ##STR932##                                  567                                                                                     ##STR933##   O  O O                                                                                   ##STR934##                                  568      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR935##                                  569      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR936##                                  570                                                                                     ##STR937##   O  O O                                                                                   ##STR938##                                  571                                                                                     ##STR939##   O  O O                                                                                   ##STR940##                                  572      C.sub.3 H.sub.7 -i                                                                          O  O NH                                                                                  ##STR941##                                  573      C.sub.3 H.sub.7 -i                                                                          O  O NH                                                                                  ##STR942##                                  574      C.sub.3 H.sub.7 -i                                                                          O  O NH                                                                                  ##STR943##                                  575      C.sub.3 H.sub.7 -i                                                                          O  O NH                                                                                  ##STR944##                                  576      C.sub.3 H.sub.7 -i                                                                          O  O NCH.sub.3                                                                           ##STR945##                                  577      C.sub.3 H.sub.7 -i                                                                          O  O NCH.sub.3                                                                           ##STR946##                                  578      C.sub.3 H.sub.7 -i                                                                          O  O NCH.sub.3                                                                           ##STR947##                                  579                                                                                     ##STR948##   O  O NH                                                                                  ##STR949##                                  580                                                                                     ##STR950##   O  O NH                                                                                  ##STR951##                                  581                                                                                     ##STR952##   O  O NCH.sub.3                                                                           ##STR953##                                  582                                                                                     ##STR954##   O  O NCH.sub.3                                                                           ##STR955##                                  583      C.sub.3 H.sub.7 -i                                                                          O  O S                                                                                   ##STR956##                                  584      C.sub.3 H.sub.7 -i                                                                          O  O S                                                                                   ##STR957##                                  585      C.sub.3 H.sub.7 -i                                                                          O  O S                                                                                   ##STR958##                                  586      C.sub.3 H.sub.7 -i                                                                          O  O S                                                                                   ##STR959##                                  587      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR960##                                  588                                                                                     ##STR961##   O  O O                                                                                   ##STR962##                                  589      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR963##                                  590      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR964##                                  591                                                                                     ##STR965##   O  O O                                                                                   ##STR966##                                  592      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR967##                                  593      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR968##                                  594      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR969##                                  595                                                                                     ##STR970##   O  O O                                                                                   ##STR971##                                  596                                                                                     ##STR972##   O  O O                                                                                   ##STR973##                                  597      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR974##                                  598      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR975##                                  599                                                                                     ##STR976##   O  O O                                                                                   ##STR977##                                  600      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR978##                                  601      C.sub.3 H.sub.7 -i                                                                          O  O O                                                                                   ##STR979##                                  __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________     ##STR980##                                                                   Compound                              Melting Point (°C.) or           No.   R.sup.1       Z.sup.1                                                                         Z.sup.2                                                                         Z.sup.3                                                                         A           Reflactive Index (n.sub.D.sup.20)       __________________________________________________________________________    602   C.sub.4 H.sub.9 -t                                                                          O O O                                                                                ##STR981## not determined                          603   C.sub.4 H.sub.9 -t                                                                          O O O                                                                                ##STR982##                                         604   C.sub.4 H.sub.9 -t                                                                          O O O                                                                                ##STR983##                                         605   C.sub.4 H.sub.9 -t                                                                          O O O                                                                                ##STR984## 1.4784                                  606   C.sub.4 H.sub.9 -t                                                                          O O O                                                                                ##STR985## 1.5109                                  607   C.sub.4 H.sub.9 -t                                                                          O O O                                                                                ##STR986## not determined                          608   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR987##                                         609   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR988##                                         610   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR989##                                         611                                                                                  ##STR990##   O O O                                                                                ##STR991##                                         612                                                                                  ##STR992##   O O O                                                                                ##STR993##                                         613                                                                                  ##STR994##   O O O                                                                                ##STR995##                                         614                                                                                  ##STR996##   O O O                                                                                ##STR997##                                         615                                                                                  ##STR998##   S O O                                                                                ##STR999##                                         616                                                                                  ##STR1000##  S O O                                                                                ##STR1001##                                        617                                                                                  ##STR1002##  O S O                                                                                ##STR1003##                                        618                                                                                  ##STR1004##  O S O                                                                                ##STR1005##                                        619                                                                                  ##STR1006##  S S O                                                                                ##STR1007##                                        620                                                                                  ##STR1008##  S S O                                                                                ##STR1009##                                        621   C.sub.3 H.sub.7 -i                                                                          O O S                                                                                ##STR1010##                                        622   C.sub.3 H.sub.7 -i                                                                          O O S                                                                                ##STR1011##                                        623                                                                                  ##STR1012##  O O S                                                                                ##STR1013##                                        624                                                                                  ##STR1014##  O O S                                                                                ##STR1015##                                        625                                                                                  ##STR1016##  O O S                                                                                ##STR1017##                                        626                                                                                  ##STR1018##  O O O                                                                                ##STR1019##                                        627                                                                                  ##STR1020##  O O O                                                                                ##STR1021##                                        628                                                                                  ##STR1022##  O O O                                                                                ##STR1023##                                        629                                                                                  ##STR1024##  O O O                                                                                ##STR1025##                                        630                                                                                  ##STR1026##  O O O                                                                                ##STR1027##                                        631                                                                                  ##STR1028##  O O O                                                                                ##STR1029##                                        632                                                                                  ##STR1030##  O O O                                                                                ##STR1031##                                        633                                                                                  ##STR1032##  O O O                                                                                ##STR1033##                                        634   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR1034##                                        635                                                                                  ##STR1035##  O O O                                                                                ##STR1036##                                        636   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR1037##                                        637                                                                                  ##STR1038##  O O O                                                                                ##STR1039##                                        638   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR1040##                                        639   C.sub.3 H.sub.7 -i                                                                          O O O                                                                                ##STR1041##                                        __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________     ##STR1042##                                                                                                      Melting Point (°C.) or             Compound No.                                                                          R.sup.1       Z.sup.3                                                                         A           Reflactive Index (n.sub.D.sup.20)         __________________________________________________________________________    640     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1043##                                          641     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1044##                                          642     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1045##                                          643     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1046##                                                                              153-155                                   644     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1047##                                          645     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1048##                                          646                                                                                    ##STR1049##  O                                                                                ##STR1050##                                          647                                                                                    ##STR1051##  O                                                                                ##STR1052##                                          648                                                                                    ##STR1053##  O                                                                                ##STR1054##                                                                              157-160                                   649                                                                                    ##STR1055##  O                                                                                ##STR1056##                                          650                                                                                    ##STR1057##  O                                                                                ##STR1058##                                          651                                                                                    ##STR1059##  O                                                                                ##STR1060##                                          652                                                                                    ##STR1061##  O                                                                                ##STR1062##                                          653                                                                                    ##STR1063##  O                                                                                ##STR1064##                                          654                                                                                    ##STR1065##  O                                                                                ##STR1066##                                          655                                                                                    ##STR1067##  O                                                                                ##STR1068##                                          656                                                                                    ##STR1069##  O                                                                                ##STR1070##                                          657                                                                                    ##STR1071##  O                                                                                ##STR1072##                                          658                                                                                    ##STR1073##  O                                                                                ##STR1074##                                          659                                                                                    ##STR1075##  O                                                                                ##STR1076##                                          660                                                                                    ##STR1077##  O                                                                                ##STR1078##                                          661                                                                                    ##STR1079##  S                                                                                ##STR1080##                                          662                                                                                    ##STR1081##  S                                                                                ##STR1082##                                          663                                                                                    ##STR1083##  S                                                                                ##STR1084##                                          664                                                                                    ##STR1085##  O                                                                                ##STR1086##                                          665                                                                                    ##STR1087##  O                                                                                ##STR1088##                                          __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________     ##STR1089##                                                                                                       Melting Point (°C.) or            Compound No.                                                                          R.sup.1       Z.sup.3                                                                         A            Reflactive Index (n.sub.D.sup.20)        __________________________________________________________________________    666     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1090##                                          667     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1091##                                          668     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1092##                                          669     C.sub.4 H.sub.9 -t                                                                          O                                                                                ##STR1093##                                          670     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1094##                                          671     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1095##                                          672     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1096## 1.5111                                   673                                                                                    ##STR1097##  O                                                                                ##STR1098##                                          674                                                                                    ##STR1099##  O                                                                                ##STR1100##                                          675                                                                                    ##STR1101##  O                                                                                ##STR1102##                                          676                                                                                    ##STR1103##  O                                                                                ##STR1104##                                          677                                                                                    ##STR1105##  O                                                                                ##STR1106##                                          678                                                                                    ##STR1107##  O                                                                                ##STR1108##                                          679                                                                                    ##STR1109##  O                                                                                ##STR1110##                                          680                                                                                    ##STR1111##  O                                                                                ##STR1112##                                          681                                                                                    ##STR1113##  O                                                                                ##STR1114##                                          682                                                                                    ##STR1115##  O                                                                                ##STR1116##                                          683                                                                                    ##STR1117##  O                                                                                ##STR1118##                                          684                                                                                    ##STR1119##  O                                                                                ##STR1120##                                          685                                                                                    ##STR1121##  O                                                                                ##STR1122##                                          686                                                                                    ##STR1123##  O                                                                                ##STR1124##                                          687                                                                                    ##STR1125##  O                                                                                ##STR1126##                                          688                                                                                    ##STR1127##  O                                                                                ##STR1128##                                          689                                                                                    ##STR1129##  O                                                                                ##STR1130##                                          690                                                                                    ##STR1131##  O                                                                                ##STR1132##                                          691                                                                                    ##STR1133##  O                                                                                ##STR1134##                                          692                                                                                    ##STR1135##  S                                                                                ##STR1136##                                          693                                                                                    ##STR1137##  S                                                                                ##STR1138##                                          694                                                                                    ##STR1139##  S                                                                                ##STR1140##                                          695     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1141##                                          696     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1142##                                          697                                                                                    ##STR1143##  O                                                                                ##STR1144##                                          698                                                                                    ##STR1145##  O                                                                                ##STR1146##                                          __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________     ##STR1147##                                                                                                  Melting Point (°C.) or                 Compound No.                                                                          R.sup.1  Z.sup.3                                                                         A            Reflactive Index (n.sub.D.sup.20)             __________________________________________________________________________    699     C.sub.4 H.sub.9 -t                                                                     O                                                                                ##STR1148##                                               700     C.sub.4 H.sub.9 -t                                                                     O                                                                                ##STR1149##                                               701     C.sub.4 H.sub.9 -t                                                                     O                                                                                ##STR1150##                                               702     C.sub.4 H.sub.9 -t                                                                     O                                                                                ##STR1151##                                               703     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1152##                                               704     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1153##                                               705     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1154##                                               706                                                                                    ##STR1155##                                                                           O                                                                                ##STR1156##                                               707                                                                                    ##STR1157##                                                                           O                                                                                ##STR1158##                                               708                                                                                    ##STR1159##                                                                           O                                                                                ##STR1160## 128-130                                       709                                                                                    ##STR1161##                                                                           O                                                                                ##STR1162##                                               710                                                                                    ##STR1163##                                                                           O                                                                                ##STR1164##                                               711                                                                                    ##STR1165##                                                                           O                                                                                ##STR1166##                                               712     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1167##                                               713     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1168##                                               714     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1169##                                               715                                                                                    ##STR1170##                                                                           O                                                                                ##STR1171##                                               716                                                                                    ##STR1172##                                                                           O                                                                                ##STR1173##                                               717     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1174##                                               718     C.sub.3 H.sub.7 -i                                                                     O                                                                                ##STR1175##                                               719                                                                                    ##STR1176##                                                                           O                                                                                ##STR1177##                                               720                                                                                    ##STR1178##                                                                           O                                                                                ##STR1179##                                               721     C.sub.3 H.sub.7 -i                                                                     S                                                                                ##STR1180##                                               722     C.sub.3 H.sub.7 -i                                                                     S                                                                                ##STR1181##                                               723     C.sub.3 H.sub.7 -i                                                                     S                                                                                ##STR1182##                                               724                                                                                    ##STR1183##                                                                           S                                                                                ##STR1184##                                               725                                                                                    ##STR1185##                                                                           S                                                                                ##STR1186##                                               726                                                                                    ##STR1187##                                                                           S                                                                                ##STR1188##                                               __________________________________________________________________________

                                      TABLE 10                                    __________________________________________________________________________     ##STR1189##                                                                                             Melting Point (°C.) or                      Compound No.                                                                          R.sup.1                                                                              Z.sup.3                                                                         A         Reflactive Index (n.sub.D.sup.20)                  __________________________________________________________________________    727     C.sub.4 H.sub.9 -t                                                                   O                                                                                ##STR1190##                                                 728     C.sub.4 H.sub.9 -t                                                                   O                                                                                ##STR1191##                                                 729     C.sub.4 H.sub.9 -t                                                                   O                                                                                ##STR1192##                                                 730     C.sub.3 H.sub.7 -i                                                                   O                                                                                ##STR1193##                                                 731     C.sub.3 H.sub.7 -i                                                                   O                                                                                ##STR1194##                                                 732     C.sub.3 H.sub.7 -i                                                                   O                                                                                ##STR1195##                                                 733                                                                                    ##STR1196##                                                                         O                                                                                ##STR1197##                                                 734                                                                                    ##STR1198##                                                                         O                                                                                ##STR1199##                                                 735                                                                                    ##STR1200##                                                                         O                                                                                ##STR1201##                                                 736     C.sub.3 H.sub.7 -i                                                                   S                                                                                ##STR1202##                                                 737     C.sub.3 H.sub.7 -i                                                                   S                                                                                ##STR1203##                                                 738                                                                                    ##STR1204##                                                                         S                                                                                ##STR1205##                                                 __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________     ##STR1206##                                                                                                       Melting Point (°C.) or            Compound No.                                                                          R.sup.1       Z.sup.3                                                                         A            Reflactive Index (n.sub.D.sup.20)        __________________________________________________________________________    739                                                                                    ##STR1207##  O                                                                                ##STR1208##                                          740     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1209##                                          741     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1210## 150-151                                  742                                                                                    ##STR1211##  O                                                                                ##STR1212##                                          743                                                                                    ##STR1213##  O                                                                                ##STR1214##                                          744                                                                                    ##STR1215##  O                                                                                ##STR1216##                                          745     C.sub.3 H.sub.7 -i                                                                          S                                                                                ##STR1217##                                          746                                                                                    ##STR1218##  S                                                                                ##STR1219##                                          747     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1220##                                          748     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1221##                                          749     C.sub.3 H.sub.7 -i                                                                          O                                                                                ##STR1222##                                          __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________     ##STR1223##                                                                                                     Melting Point (°C.) or              Compound No.                                                                          R.sup.1                                                                              R.sup.4                                                                           R.sup.5                                                                          R.sup.6                                                                          A         Reflactive Index (n.sub.D.sup.20)          __________________________________________________________________________    750                                                                                    ##STR1224##                                                                         H   H  CH.sub.3                                                                          ##STR1225##                                                                            not determined                             751     C.sub.4 H.sub.9 -t                                                                   H   H  CH.sub.3                                                                          ##STR1226##                                                                            46-50                                      752     C.sub.3 H.sub.7 -i                                                                   H   H  CH.sub.3                                                                          ##STR1227##                                         753                                                                                    ##STR1228##                                                                         H   H  CH.sub.3                                                                          ##STR1229##                                         754     C.sub.4 H.sub.9 -t                                                                   H   H  CH.sub.3                                                                          ##STR1230##                                         755     C.sub.3 H.sub.7 -i                                                                   H   H  CH.sub.3                                                                          ##STR1231##                                         756                                                                                    ##STR1232##                                                                         H   H  CH.sub.3                                                                          ##STR1233##                                         757     C.sub.4 H.sub.9 -t                                                                   H   H  CH.sub.3                                                                          ##STR1234##                                         758     C.sub.3 H.sub.7 -i                                                                   H   H  CH.sub.3                                                                          ##STR1235##                                         759                                                                                    ##STR1236##                                                                         H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1237##                                         760     C.sub.4 H.sub.9 -t                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1238##                                         761     C.sub.3 H.sub.7 -i                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1239##                                         762                                                                                    ##STR1240##                                                                         H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1241##                                         763     C.sub.4 H.sub.9 -t                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1242##                                         764     C.sub.3 H.sub.7 -i                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1243##                                         765                                                                                    ##STR1244##                                                                         H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1245##                                         766     C.sub.4 H.sub.9 -t                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1246##                                         767     C.sub.3 H.sub.7 -i                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                          ##STR1247##                                         768                                                                                    ##STR1248##                                                                         C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1249##                                                                            150-152                                    769     C.sub.4 H.sub.9 -t                                                                   C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1250##                                         770     C.sub.3 H.sub.7 -i                                                                   C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1251##                                                                            154-157                                    771                                                                                    ##STR1252##                                                                         C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1253##                                         772     C.sub.4 H.sub.9 -t                                                                   C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1254##                                         773     C.sub.3 H.sub.7 -i                                                                   C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1255##                                         774                                                                                    ##STR1256##                                                                         C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1257##                                         775     C.sub.4 H.sub.9 -t                                                                   C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1258##                                         776     C.sub.3 H.sub.7 -i                                                                   C.sub.3 H.sub.7 -i                                                                H  H                                                                                 ##STR1259##                                         __________________________________________________________________________

The compounds represented by Formula [I] according to the presentinvention can be prepared, for example, in the following manner.##STR1260## wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, Z¹, Z², Z³, Q, m,and n have the same meanings as defined above.

The compounds represented by Formula [I] according to the presentinvention can be prepared by reacting an amino acid derivativerepresented by Formula [IX] or the amino acid derivative wherein thecarboxyl group is activated, with an amine represented by Formula [X] inthe presence of a base and/or a catalyst, if necessary.

In the present reaction, as the amino acid derivative represented byFormula [IX] with an activated carboxyl group, there can be mentioned,for example, an acid halide such as an acid chloride, an acid anhydridederived from the two molecules of the amino acid derivatives representedby Formula [IX], a mixed acid anhydride derived from the amino acidderivative represented by Formula [IX] and other acid or an O-alkylcarbonic acid, and an activated ester such as p-nitrophenyl ester,2-tetrahydropyranyl ester, and 2-pyridyl ester and the like. These aminoacid derivatives with activated carboxyl groups can be synthesizedaccording to conventional methods [for example, see Methoden derOrganischen Chemie, Vol. 15, No. 2, from page 2; Georg Thieme VerlagStuttgart: 1974; Chemische Berichte, Vol. 38, page 605 (1905); Journalof the American Chemical Society, Vol. 74, page 676 (1952); and Journalof the American Chemical Society, Vol. 86, page 1839 (1964)].

In addition, it is also possible to perform the present reaction using acondensing agent such as N,N'-dicyclohexylcarbodiimide,carbonyldiimidazole, 2-chloro- 1,3-dimethylimidazolium chloride, or thelike.

The present reaction can be performed in a conventional solvent: thissolvent can be any solvent that does not hinder the reaction, forexample, hydrocarbons such as pentane, hexane, heptane, cyclohexane,petroleum ether, ligroin, benzene, toluene, xylene and the like,halogenated hydrocarbons such as dichloromethane, dichloroethane,chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene and thelike, ethers such as diethyl ether, diisopropyl ether, ethylene glycoldimethyl ether, tetrahydrofuran, dioxane and the like, ketones such asacetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutylketone and the like, esters such as methyl acetate, ethyl acetate andthe like, nitriles such as acetonitrile, propionitrile, benzonitrile andthe like aprotic polar solvents such as dimethylsulfoxide,dimethylformamide, sulfolane and the like, and mixed solvents combiningsolvents selected from the aforementioned.

The base can be any type of base generally used in this type ofreaction. For example, there can be mentioned hydroxides of alkalinemetals such as sodium hydroxide, potassium hydroxide and the like,hydroxides of alkaline earth metals such as calcium hydroxide and thelike, carbonates of alkaline metals such as sodium carbonate, potassiumcarbonate and the like, bicarbonates of alkaline metals such as sodiumbicarbonate, potassium bicarbonate and the like, organic bases such astriethylamine, trimethylamine, dimethylaniline, pyridine,N-methylmorpholine, N-methylpiperidine, 1,5-diazabicyclo [4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU), and thelike, and preferably tertiary amines such as triethylamine, pyridine,N-methylpiperidine and the like.

As the catalyst, there can be mentioned 4-dimethylaminopyridine,1-hydroxybenzotriazole, dimethylformamide and the like. The presentreaction is carried out at a temperature of -75° C. to 100° C.,preferably -60° C. to 40° C. The reaction time is preferably 1 to 20hours.

Furthermore, compounds represented by formula [IX] as the startingmaterial can generally be synthesized by conventional methods [forexample, see Methoden der Organischen Chemie, Vol. 15, No. 2, from page2; Georg Thieme Verlag Stuttgart: 1974; Chemistry of the Amino Acids,vol. 2, page 891; John Wiley & Sons, New York (1964); and Journal of theAmerican Chemical Society, Vol. 79, page 4686 (1957)]. Variousmanufacturing methods for compounds [X] can also be considered such asthose methods stated in Japanese patent application First PublicationNo. Sho 63-146876, Tetrahedron Letters, page 21, 1973, and JapanesePatent Application, First Publication, No. Hei 5-271206). ##STR1261##wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, Z¹, Z², Z³, Q, m n have the samemeanings as defined above, and Y represents a halogen atom, a4,6-dimenylpyrimidinylthio group, an R¹ OC(O)O-- group, or an--ON═C(CN)Ph group (in which Ph represents a phenyl group).

Compounds of the present invention represented by Formula [I] can bemanufactured by means of reacting the compound represented by Formula[XI] with an amine represented by Formula [XII] or the salt of the aminederivative with an inorganic acid such as hydrochloride and the like, ora salt of the amine derivative with an organic acid such as rosylate andthe like, in the presence of a base when required.

The present reaction can be performed in a conventional solvent: thissolvent can be any solvent that does not hinder the reaction, forexample, hydrocarbons such as pentane, hexane, heptane, cyclohexane,petroleum ether, ligroin, benzene, toluene, xylene and the like,halogenated hydrocarbons such as dichloromethane, dichloroethane,chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene and thelike, ethers such as diethyl ether, diisopropyl ether, ethylene glycoldimethyl ether, tetrahydrofuran, dioxane and the like, ketones such asacetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutylketone and the like, esters such as methyl acetate, ethyl acetate andthe like, nitriles such as acetonitrile, propionitrile, benzonitrile andthe like, aprotic polar solvents such as dimethylsulfoxide,dimethylformamide, sulfolane and the like, water, and mixed solventscombining solvents selected from the aforementioned.

The base can be any type of base generally used in this type ofreaction. For example, there can be mentioned hydroxides of alkalinemetals such as sodium hydroxide, potassium hydroxide and the like,hydroxides of alkaline earth metals such as calcium hydroxide and thelike, carbonates of alkaline metals such as sodium carbonate, potassiumcarbonate and the like, bicarbonates of alkaline metals such as sodiumbicarbonate, potassium bicarbonate and the like, organic bases such astriethylamine, trimethylamine, dimethylaniline, N-methylmorpholine,pyridine, N-methylpiperidine, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN),1,8-diazabicyclo [5.4.0]-undec-7-ene (DBU), and the like, and preferablytertiary amines such as triethylamine, pyridine, N-methylpiperidine andthe like. The present reaction is carried out at a temperature of -20°C. to 100° C., preferably 0° C. to 40° C. The reaction time ispreferably 30 minutes to 20 hours.

Compounds represented by Formula [XII] as the starting materialrepresent novel compounds, and can be manufactured, for example, bymeans of treating carbamates of compounds [I] synthesized by theprocedure of preparation process A using a conventional process forremoving the amino protecting group of the amino acid such as catalyticreduction, or by treating with acids such as liquid hydrofluoric acid,sulfonic acids, hydrochloric acid, hydrobromic acid, formic acid and thelike.

In the following, synthesis examples of amino-acid amide derivatives,which are novel intermediates of the compounds of the present inventionrepresented by Formulae [X] and [XII], are provided as referenceexamples.

REFERENCE EXAMPLE 1 Synthesis of 2-(4-cyanophenoxy)-1-methylethylamine(Intermediate Compound No. 1)

293 g of ammonium acetate and 16.7 g of sodium cyanoborohydride wereadded to a solution containing 66.5 g of 4-cyanophenoxyacetone dissolvedin 1500 mL of methanol, and the resultant mixture was stirred for 30hours at room temperature. The reaction mixture was then concentratedunder reduced pressure, and acidified with concentrated hydrochloricacid. 500 mL of diethyl ether and 300 mL of water were then addedthereto. Subsequently, the resultant water layer was made basic with a5% aqueous solution of sodium hydroxide, the solution was extracted with1000 mL of diethyl ether, and then washed with water. The organic layerwas then dried over anhydrous sodium sulfate, and the diethyl ether wasremoved under reduced pressure. The obtained residue was distilled underreduced pressure to yield 13.0 g of the desired product (19%). Boilingpoint: 132° C./0.26 mmHg.

REFERENCE EXAMPLE 2 Synthesis of2-(4-chloro-2-methylphenoxy)-1-methylethylamine (Intermediate CompoundNo. 2)

120 g of ammonium acetate and 9.8 g of sodium cyanoborohydride wereadded to a solution containing 31 g of (4-chloro-2-methylphenoxy)acetonedissolved in 700 mL of methanol, and the resultant mixture was stirredfor 20 hours at room temperature. After the reaction mixture wasconcentrated under reduced pressure, 180 mL of concentrated hydrochloricacid and 100 mL of water were added to the residue. The whole mixturewas stirred for 1 hour, and then extracted with 300 mL of diethyl ether.The water layer was alkalifled using a 5% aqueous solution of sodiumhydroxide, and then extracted with 500 mL of ethyl acetate. The organiclayer was washed with water, dried over anhydrous magnesium sulfate, andthen concentrated under reduced pressure. A fraction possessing a lowboiling point was removed from the obtained oily products to afford 25 g(yield 81%) of the desired product. Refractive index: 1.5360.

REFERENCE EXAMPLE 3 Synthesis of 2-(4-chlorophenoxy)-1-methylpropylamine(Intermediate Compound No. 3)

82 g of ammonium acetate and 6.7 g of sodium cyanoborohydridc were addedto a solution containing 21 g of 3-(4-chlorophenoxy)-2-butanonedissolved in 500 mL of methanol, and the reaction mixture was stirredfor 20 hours at room temperature. The reaction mixture was thenconcentrated under reduced pressure, and 180 mL of concentratedhydrochloric acid and 100 mL of water were added to the residue. Thewhole mixture was extracted with 300 mL of diethyl ether. The obtainedwater layer was alkalifled using a 5% aqueous solution of sodiumhydroxide, and then extracted with 500 mL of ethyl acetate. The organiclayer was washed with water, dried over anhydrous magnesium sulphate,and then concentrated under reduced pressure. A fraction possessing alow boiling point was removed from the obtained oily products to afford18 g (yield 86%) of the desired product. Refractive index: 1.5360.

REFERENCE EXAMPLE 4 Synthesis of 1-methyl-2-(2-methylphenoxy)ethylamine(Intermediate Compound No. 4)

A solution containing 36 g of 2-(2-methylphenoxy)acetone oxime O-methylether dissolved in 150 mL of dimethoxyethane was added dropwise to asuspension containing 13 g of sodium borohydride in 500 mL ofdimethoxyethane at room temperature. After the mixture was stirred for15 minutes at room temperature, a solution containing 66 g oftrifluoroborane diethyl ether complex dissolved in 100 mL ofdimethoxyethane was added dropwise to the mixture at room temperature.The reaction mixture was stirred for 30 minutes at room temperature andthen refluxed for 3 hours. The resultant mixture was allowed to sit andcool naturally to room temperature and then acidified using a 10%hydrochloric acid. The dimethoxyethane layer was concentrated andcombined with the water layer. The mixture was alkalified using sodiumcarbonate, and then extracted with dichloromethane, followed by washingwith water. The organic layer was dried over anhydrous magnesiumsulfate, and then the dichloromethane was removed under reducedpressure. The residue was distilled under reduced pressure to obtain 6.4g (yield 21%) of the desired product. Boiling point: 65° C./0.08 mmHg.

REFERENCE EXAMPLE 5 Synthesis of 2-(4-cyanophenoxy)- 1-methylethylamine(Intermediate Compound No. 1)

50.0 g of 2-amino-1-propanol was added dropwise to a stirred mixture of29.3 g of 60% sodium hydride and 300 mL of N,N-dimethylformamide at 0°C. After the reaction mixture was stirred for 30 minutes at 0° C., asolution containing 121.2 g of 4-bromobenzonitrile dissolved inN,N-dimethylformamide was added dropwise to the reaction mixture. Theresultant mixture was stirred for 20 hours at room temperature. Aftercompletion of the reaction, the resultant mixture was poured into waterand extracted with ethyl acetate. The organic layer was washed withwater and then dried over anhydrous magnesium sulfate. The ethyl acetatewas removed under reduced pressure. The residue was distilled underreduced pressure to obtain 48.0 g of the desired product (yield 41%).Boiling point: 132° C./0.26 mmHg.

REFERENCE EXAMPLE 6 Synthesis of(-)-2-(4-cyanophenoxy)-1-methylethylamine (Intermediate Compound No. 5)

25.0 g of R-(-)-2-amino-1-propanol was added dropwise to a stirredmixture of 14.0 g of 60% sodium hydride and 200 mL ofN,N-dimethylformamide at a temperature of 5° C. to 10° C. After thereaction mixture was stirred for 30 minutes, a solution containing 45.0g of 4-chlorobenzonitrile dissolved in N,N-dimethylformamide was addeddropwise to the reaction mixture. The reaction mixture was stirred for20 hours at room temperature. After completion of the reaction, thereaction mixture was poured into water and extracted with ethyl acetate.The organic layer was washed with water and then dried over anhydrousmagnesium sulfate. The ethyl acetate was removed under reduced pressure.The residue was distilled under reduced pressure to obtain 33.0 g of thedesired product (yield: 56%). Boiling point: 60°-66° C./0.08 mmHg,[α]D²⁰ -15.7° (C1.0 CH₃ OH).

REFERENCE EXAMPLE 7 Synthesis of 1-methyl-2-(2-pyrimidyloxy)ethylamine(Intermediate Compound No. 6)

2.0 g of 2-amino-1-propanol was added dropwise to a stirred mixture of1.3 g of 60% sodium hydride and 30 mL of N,N-dimethylformamide at roomtemperature. After the reaction mixture was stirred for 30 minutes, asolution containing 3.7 g of 2-chloropyrimidine dissolved inN,N-dimethylformamide was added dropwise to the reaction mixture. Themixture was stirred for 2 hours at 100° C. After completion of thereaction, the reaction mixture was cooled. The solids were filtered off.The solvent in the filtrate was removed under reduced pressure. Theresidue was purified by column chromatography on silica gel to obtain2.1 g of the desired product (yield: 50%). Refractive index: 1.5481.

REFERENCE EXAMPLE 8 Synthesis of 1-methyl-2-(4-pyridyloxy)ethylamine(Intermediate Compound No. 7)

6.2 g of 2-amino-1-propanol was added dropwise to a stirred mixture of4.0 g of 60% sodium hydride and 50 mL of N,N-dimethylformamide at 5°C.-10° C. After the reaction mixture was stirred for 30 minutes, 12.5 gof 4-chloropyridine hydrochloride in limited amounts was added to thereaction mixture. The mixture was stirred for 20 hours at roomtemperature. After completion of the reaction, the solids were filteredoff. The solvent in the filtrate was removed under reduced pressure. Theresidue was purified by column chromatography on silica gel to obtain3.8 g of the desired product (yield: 30%). Refractive index: 1.5469.

Specific examples of intermediate [X] obtained through the operations ofReference Examples 1 to 8 are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                         ##STR1262##                                                                  Inter-                                                                        mediate                                                                       Com-                        Reflactive Index (n.sub.D .sup.20)                pound                       or                                                No.     R.sup.6                                                                              Xp           Boiling Point (°C./mmHg)                   ______________________________________                                         8      H      2-OCH.sub.3  96.5/0.15                                          9      H      3-OCH.sub.3  1.5158                                            10      H      4-OCH.sub.3    95/0.10                                         11      H      2-CN         1.5566                                            12      H      3-CN         1.5409                                            13      H      2-F            70/0.22                                         14      H      3-F            74/0.15                                         15      H      2-NO.sub.2   1.5582                                            16      H      2,4-Cl.sub.2 1.5475                                            17      H      3,4-Cl.sub.2  107/0.16                                         18      H      3,5-Cl.sub.2  100/0.12                                         19      H      3,4-(OCH.sub.3).sub.2                                                                      1.5361                                            20      H      3,5-(OCH.sub.3).sub.2                                                                      12.5/0.10                                         21      CH.sub.3                                                                             4-CN         1.5480                                            22      CH.sub.3                                                                             4-NO.sub.2   1.6263                                            ______________________________________                                    

REFERENCE EXAMPLE 9

Synthesis of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamidehydrochloride (Intermediate Compound No. 23)

Hydrogen chloride gas was introduced into a solution containing 3.7 g ofN2-tert-butoxycarbonyl-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide dissolved in 100 mL ofmethylene chloride for 1 hour at room temperature. After completion ofthe reaction, the methylene chloride was removed under reduced pressure,thus obtaining a crude crystal. The crude crystal was washed withacetone to afford 3.1 g of the desired product (yield: 100%). Meltingpoint: 59°-63° C.

REFERENCE EXAMPLE 10 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-isoleucinamide (IntermediateCompound No. 24)

Hydrogen chloride gas was introduced into a solution containing 15.0 gof N² -tert-butoxycarbonyl-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-isoleucinamide dissolved in 300 mLof methylene chloride for 1 hour at room temperature. After completionof the reaction, the methylene chloride was removed under reducedpressure, thus obtaining a crude crystal. 200 ml of a saturated aqueoussolution of sodium bicarbonate and 200 ml of methylene chloride wereadded to the crude crystal, and the mixture was stirred for 30 minutesand extracted with methylene chloride. The organic layer was washed withwater, and dried over anhydrous sodium sulfate. The methylene chloridewas removed under reduced pressure. The obtained crude product waswashed with acetone to afford 10.0 g of the desired product (yield:90%). Melting point: 64°-67° C.

Specific examples of Intermediate [XII] obtained through the operationsof Reference Examples 9 and 10 are shown in Table 14.

                  TABLE 14                                                        ______________________________________                                         ##STR1263##                                                                  Inter-                                                                        mediate                      Reflactive Index (n.sub.D .sup.20)               Com-                         or                                               pound                        Boiling Point                                    No.    R.sup.2 Q             (°C./mmHg)                                ______________________________________                                        25     C.sub.3 H.sub.7 -i                                                                     ##STR1264##  73-75                                            26     C.sub.2 H.sub.5                                                                        ##STR1265##  43-44                                            27     C.sub.2 H.sub.5                                                                        ##STR1266##  1.5391                                           28     C.sub.3 H.sub.7                                                                        ##STR1267##  1.5299                                           29     C.sub.4 H.sub.9 -t                                                                     ##STR1268##  1.5251                                           30     C.sub.3 H.sub.7 -i                                                                     ##STR1269##  1.5250                                           ______________________________________                                    

The Best Mode for Carrying Out the Invention

The methods for producing the compounds according to the presentinvention as well as the use of the compounds will be described indetail in the following Synthesis Examples.

SYNTHESIS EXAMPLE 1 Synthesis of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-nitrophenoxy)ethyl]-L-valinamide (Compound No. 16)

0.5 g of N-methylpiperidine was added to a solution containing 1.1 g ofN-tert-butoxycarbonyl-L-valine dissolved in 40 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 0.7 g of isobutyl chloroformate was added to the mixture at-40° C., and stirred for 1 hour at -20° C. 1 g of1-methyl-2-(4-nitrophenoxy)ethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 15 hours atroom temperature. Water was subsequently added to the reaction mixture.After the dichloromethane layer was successively washed with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue, which was a crude crystal,was purified by column chromatography on silica gel, thus obtaining 0.7g of the desired product in the form of a yellow powder (yield: 55%).

SYNTHESIS EXAMPLE 2 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-isopropenyloxycarbonyl-L-valinamide (Compound No. 77)

0.6 g of N-methylmorpholine, and subsequently 0.4 g of isopropylchloroformate were added to a solution containing 0.9 g of N¹-[2-(4-cyanophenoxy)-1-methylethyl]L-valinamide hydrochloride dissolvedin 50 ml of methylene chloride at -15° C. The mixture was allowed to sitand warm naturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe dichloromethane layer was washed with water, the organic layer wasdried over anhydrous magnesium sulfate and then the methylene chloridewas removed under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.23 g of the desiredproduct in the form of colorless grains (yield: 13% ).

SYNTHESIS EXAMPLE 3 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N² -phenoxycarbonyl-L-valinamide(Compound No. 107)

1.3 g of N-methylpiperidine was added to a solution containing 3 g ofN-phenoxycarbonyl-L-valine dissolved in 50 mL of methylene chloride, at-20° C. After the mixture was stirred for 10 minutes at the sametemperature, 1.7 g of isobutyl chloroformate was added to the mixture at-40° C., and stirred for 1 hour at -20° C. 2.2 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature, with stirring, and stirred for 20 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed successively with a 5% aqueoussolution of sodium bicarbonate and water, the organic layer was driedover anhydrous magnesium sulfate and the methylene chloride was removedunder reduced pressure. The residue, which was a crude crystal, waspurified by column chromatography on silica gel, thus obtaining 1.1 g ofthe desired product in the form of a white powder (yield: 22%).

SYNTHESIS EXAMPLE 4 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-isoleucinamide (Compound No. 228)

1.3 g of N-methylpiperidine was added to a solution containing 3 ofN-tert-butoxycarbonyl-L-isoleucine dissolved in 60 mL of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 1.8 g of isobutyl chloroformate was added to themixture at -40° C., and stirred for 1 hour at -20° C. 2.3 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.6 g of the desiredproduct in the form of a white powder (yield: 12% ).

Synthesis Example 5 Synthesis of N² -tert-butoxycarbonyl-N¹-(2-phenylthioethyl)-L-valinamide (Compound No. 551)

1 g of N-methylpiperidine was added to a solution containing 2.1 g ofN-tert-butoxycarbonyl-L-valine dissolved in 40 mL of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 1.3 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 1.5 g of 2-phenylthioethylamine wasadded to this mixture at -60° C., and then the reaction mixture wasallowed to sit and warm naturally to room temperature while beingstirred, and was stirred for 20 hours at room temperature. Water wassubsequently added to the reaction mixture. After the methylene chloridelayer was washed successively with a 5% aqueous solution of sodiumbicarbonate and water, the organic layer was dried over anhydrousmagnesium sulfate and the methylene chloride was removed under reducedpressure. The residue was purified by column chromatography on silicagel, thus obtaining 0.4 g of the desired product in the form of creamyellow grains (yield: 12%).

SYNTHESIS EXAMPLE 6 Synthesis of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-nitrophenoxy)propyl]-L-valinamide (Compound No. 606)

0.5 g of N-methylpiperidine was added to a solution containing 1 g ofN-tert-butoxycarbonyl-L-valine dissolved in 40 mL of methylene chloride,at -20° C. After the mixture was stirred for 15 minutes at the sametemperature, 0.7 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 1 g of1-methyl-2-(4-nitrophenoxy)propylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue, which was an oilysubstance, was purified by column chromatography on silica gel, thusobtaining 1.1 g of the desired product in the form of yellow viscousliquid (yield: 56%).

SYNTHESIS EXAMPLE 7 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(3,5-dimethoxyphenoxy)-1-methylethyl]-L-valinamide (Compound No. 22)

0.5 g of N-methylpiperidine was added to a solution containing 1.0 g ofN-tert-butoxycarbonyl-L-valine dissolved in 100 mL of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 0.7 g of isobutyl chloroformate was added to themixture at -40° C., and stirred for 1 hour at -20° C. 1 g of2-(3,5-cyanophenoxy)-1-methylamine was added to this mixture at -60° C.,and then the reaction mixture was allowed to sit and warm naturally toroom temperature while being stirred, and was stirred for 15 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue, which was a crude crystal,was purified by column chromatography on silica gel, thus obtaining 1.3g of the desired product in the form of white powder (yield: 64%).

SYNTHESIS EXAMPLE 8 Synthesis of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(2,4,6-trichlorophenoxy)ethyl]-L-valinamide (Compound No.25)

1.7 g of N-methylpiperidine was added to a solution containing 3.8 g ofN-tert-butoxycarbonyl-L-valine dissolved in 80 mL of methylene chloride,at -20° C. After the mixture was stirred for 15 minutes at the sametemperature, 2.4 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 4.5 g of1-methyl-2-(2,4,6-trichlorophenoxy)ethylamine was added to this mixtureat -60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 4.6 g ofthe desired product in the form of a colorless needle crystal (yield:58%).

SYNTHESIS EXAMPLE 9 Synthesis of N² -isopropoxycarbonyl-N¹-[1-methyl-2-(4-nitrophenoxy)ethyl]-L-valinamide (Compound No. 45)

1.2 g of N-methylpiperidine was added to a solution containing 2.5 g ofN-isopropoxycarbonyl-L-valine dissolved in 100 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 1.7 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 2.2 g of2-(4-nitrophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.3 g of the desiredproduct in the form of a yellow vitrified substance (yield: 6%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               1.16-1.33     (6H, m)                                                         1.43-1.36     (9H, m)                                                         2.56          (1H, m)                                                         4.01          (2H, m)                                                         4.00-5.33     (3H, m)                                                         6.17          (1H, d)                                                         6.87          (2H, d)                                                         8.06          (2H, d)                                                  ______________________________________                                    

SYNTHESIS EXAMPLE 10 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-cyclohexyloxycarbonyl-L-valinamide (Compound No. 97)

0.8 g of N-methylpiperidine was added to a solution containing 2.0 g ofN-cyclohexyloxycarbonyl-L-valine dissolved in 150 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 1.1 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 1.5 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.5 g of the desiredproduct in the form of light brown powder (yield: 16%).

SYNTHESIS EXAMPLE 11 Synthesis of N¹-[1-methyl-2-(4-trifluoromethylphenoxy)ethyl]-N²-phenoxycarbonyl-L-valinamide (Compound No. 114)

1.6 g of N-methylpiperidine was added to a solution containing 4.0 g ofN-phenoxycarbonyl-L-valine dissolved in 80 ml of methylene chloride, at-20° C. After the mixture was stirred for 15 minutes at the sametemperature, 2.2 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 3.5 g of1-methyl-2-(4-trifluoromethylphenoxy)ethylamine was added to thismixture at -60° C., and then the reaction mixture was allowed to sit andwarm naturally to room temperature while being stirred, and was stirredfor 20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 2.8 g ofthe desired product in the form of a white crystal (yield: 40%).

SYNTHESIS EXAMPLE 12 Synthesis of N¹-[1-methyl-2-(4-trifluoromethoxyphenoxy)ethyl]-N²-phenoxycarbonyl-L-valinamide (Compound No. 115)

1.7 g of N-methylpiperidine was added to a solution containing 4.0 g ofN-phenoxycarbonyl-L-valine dissolved in 80 ml of methylene chloride, at-20° C. After the mixture was stirred for 15 minutes at the sametemperature, 2.3 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C.

4.0 g of 1-methyl-2-(4-trifluoromethoxyphenoxy)ethylamine was added tothis mixture at -60° C., and then the reaction mixture was allowed tosit and warm naturally to room temperature while being stirred, and wasstirred for 20 hours at room temperature. Water was subsequently addedto the reaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 3.4 g ofthe desired product in the form of a white crystal (yield: 45%).

SYNTHESIS EXAMPLE 3 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N² -phenoxycarbonyl-L-valinamide(Compound Nos. 116 and 117)

1.8 g of N-methylpiperidine was added to a solution containing 4.2 g ofN-phenoxycarbonyl-L-valine dissolved in 100 ml of methylene chloride, at-20° C. After the mixture was stirred for 10 minutes at the sametemperature, 2.4 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 3.1 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 1.0 g of a white powder.0.6 g of the obtained white powder was purified using high pressureliquid chromatography (hereinafter, referred to as "HPLC") (YMC-063-15,hexane/ethyl acetate=55/45) to separate two fractions. The ingredient ofthe first fraction possessing a short retention time was 0.3 g of awhite powder (yield: 7%) possessing 145° to 147° C. of melting point andthe ingredient of the second fraction possessing a long retention timewas 0.3 g of a white powder (yield: 7%) possessing a melting point of166° to 170° C. of melting point.

SYNTHESIS EXAMPLE 14 Synthesis of N²-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(3-methoxyphenoxycarbonyl)-L-valinamide (Compound No. 166)

1.0 g of N-methylmorpholine was added to a solution containing 1.5 g ofN¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide hydrochloridedissolved in 100 ml of methylene chloride, at -20° C. After 0.9 g of3-methoxyphenyl chloroformate was added to the mixture at -20° C., thereaction mixture was allowed to sit and warm naturally to roomtemperature while being stirred, and was stirred for 2 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and the methylene chloridewas removed under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.25 g of the desiredproduct in the form of a white plated crystal (yield: 12%).

SYNTHESIS EXAMPLE 15 Synthesis of N² -(2-chloroethoxycarbonyl)-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide (Compound No. 184)

0.5 g of N-methylpiperidine was added to a solution containing 1.1 g ofN-(2-chloroethoxycarbonyl)-L-valine dissolved in 40 ml of methylenechloride, at -20° C. After the mixture was stirred for 15 minutes at thesame temperature, 0.7 g of isobutyl chloroformate was added to themixture at -40° C., and stirred for 1 hour at -20° C. 0.9 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue, which was an oilysubstance, was purified by column chromatography on silica gel, thusobtaining 1.0 g of the desired product in the form of colorless grains(yield: 52%).

SYNTHESIS EXAMPLE 16 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(4-methylbenzyloxycarbonyl)-L-valinamide (Compound No. 195)

0.6 g of N-methylpiperidine was added to a solution containing 1.5 g ofN-(4-methylbenzyloxycarbonyl)-L-valine dissolved in 100 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 0.8 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 1.0 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue, which was a crude crystal,was purified by column chromatography on silica gel, thus obtaining 0.6g of the desired product in the form of light white powder (yield: 28%).

SYNTHESIS EXAMPLE 17 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N² -phenoxythiocarbonyl-L-valinamide(Compound No. 208)

0.4 g of N-methyhnorpholine was added to a suspension containing 1.1 gof N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide suspended in 40ml of methylene chloride, at -15° C. After 0.7 g of phenylchlorothionoformate was added to the mixture at -15° C., the reactionmixture was allowed to sit and warm naturally to room temperature whilebeing stirred, and was stirred for 15 hours at room temperature. Waterwas subsequently added to the reaction mixture. After the methylenechloride layer was washed with water, the organic layer was dried overanhydrous magnesium sulfate and the methylene chloride was removed underreduced pressure. The residue was purified by column chromatography onsilica gel, thus obtaining 1.2 g of the desired product in the form of ayellow glutinous substance (yield: 75%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               1.05          (6H, m)                                                         1.35          (3H, m)                                                         2.30          (1H, m)                                                         4.00          (2H, m)                                                         4.44          (1H, m)                                                         4.54          (1H, m)                                                         6.16, 6.25    (1H, d)                                                         7.26          (9H, m)                                                         7.51          (1H, br)                                                 ______________________________________                                    

SYNTHESIS EXAMPLE 18 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(phenylthio)thiocarbonyl-L-valinamide (Compound No. 211)

0.5 g of N-methylmorpholine was added to a suspension containing 1.4 gof N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide suspended in 40ml of methylene chloride, at -15° C. After 0.9 g of phenylchlorodithioformate was added to the mixture at -15° C., the reactionmixture was allowed to sit and, warm naturally to room temperature whilebeing stirred, and was stirred for 15 hours at room temperature. Waterwas subsequently added to the reaction mixture. After the methylenechloride layer was washed with water, the organic layer was dried overanhydrous magnesium sulfate and the methylene chloride was removed underreduced pressure. The residue was purified by column chromatography onsilica gel, thus obtaining 1.4 g of the desired product in the form of ayellow glutinous substance (yield: 66%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               0.83          (6H, m)                                                         1.30, 1.32    (3H, d)                                                         2.13          (1H, m)                                                         3.96          (2H, m)                                                         4.35          (1H, m)                                                         4.78          (1H, dd)                                                        6.04, 6.13    (1H, d)                                                         6.93, 6.98    (2H, d)                                                         7.15, 7.22    (1H, d)                                                         7.57          (7H, m)                                                  ______________________________________                                    

SYNTHESIS EXAMPLE 19 Synthesis of N¹ -(1-methyl-2-phenylthioethyl)-N²-phenoxycarbonyl-L-valinamide (Compound No. 212)

1.3 g of N-methylmorpholine was added to a suspension containing 3.0 gof N¹ -(1-methyl-2-phenylthioethyl)-L-valinamide hydrochloride suspendedin 80 ml of methylene chloride, at -15° C. After 1.9 g of phenylchloroformate was added to the mixture at -15° C., the reaction mixturewas allowed to sit and warm naturally to room temperature while beingstirred, and was stirred for 15 hours at room temperature. Water wassubsequently added to the reaction mixture. After the methylene chloridelayer was washed with water, the organic layer was dried over anhydrousmagnesium sulfate and the methylene chloride was removed under reducedpressure. The residue was purified by column chromatography on silicagel, thus obtaining 2.3 g of the desired product in the form of a whitecrystal (yield: 54%).

SYNTHESIS EXAMPLE 20 Synthesis of N¹-[2-(4-chloroanilino)-1-methylethyl]-N² -isopropoxycarbonyl-L-valinamide(Compound No. 221)

1.9 g of N-methylpiperidine was added to a solution containing 3.8 g ofN-isopropoxycarbonyl-L-valine dissolved in 80 ml of methylene chloride,at -20° C. After the mixture was stirred for 15 minutes at the sametemperature, 2.6 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 3.5 g of2-(4-chloroanilino)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 3.3 g of the desiredproduct in the form of a white crystal (yield: 47%).

SYNTHESIS EXAMPLE 21 Synthesis of2-tert-butoxycarbonylamino-N-[2-(4-chlorophenoxy)-1-methylethyl]-(2S)-butyramide(Compound No. 233)

2.0 g of N-methylpiperidine was added to a solution containing 4.1 g of(2S)-2-tert-butoxycarbonylaminobutyric acid dissolved in 60 ml ofmethylene chloride, at -20° C. After the mixture was stirred for 10minutes at the same temperature, 2.7 g of isobutyl chloroformate wasadded to the mixture at -40° C., and stirred for 1 hour at -20° C. 3.7 gof 2-(4-chlorophenoxy)-1-methylethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The obtainedcrude crystal was purified by column chromatography on silica gel, thusobtaining 5.6 g of the desired product in the form of a colorlessglutinous substance (yield: 76%).

SYNTHESIS EXAMPLE 22 Synthesis of2-tert-butoxycarbonylamino-N-[2-(4-cyanophenoxy)-1-methylethyl]-(2S)-butyramide(Compound No. 235)

0.5 g of N-methylpiperidine was added to a solution containing 1.0 g of(2S)-2-tert-butoxycarbonylaminobutyric acid dissolved in 40 ml ofmethylene chloride, at -20° C. After the mixture was stirred for 10minutes at the same temperature, 0.7 g of isobutyl chloroformate wasadded to the mixture at -20° C., and stirred for 1 hour at -20° C. 0.9 gof 2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 1.0 g ofthe desired product in the form of a glutinous substance (yield: 54%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               0.94          (3H, t)                                                         1.20-1.50     (12H, m)                                                        1.69          (2H, m)                                                         3.83-4.56     (4H, m)                                                         5.30          (1H, d)                                                         6.60          (1H, m)                                                         6.90          (2H, d)                                                         7.50          (2H, d)                                                  ______________________________________                                    

SYNTHESIS EXAMPLE 23 Synthesis of N¹-[2-(4-chlorobenzyloxy)-1methylethyl]-N²-isopropoxycarbonyl-L-valinamide (Compound No. 246)

0.5 g of N-methylpiperidine was added to a solution containing 1 g ofN-isopropoxycarbonyl-L-valine dissolved in 40 ml of methylene chloride,at -20° C. After the mixture was stirred for 15 minutes at the sametemperature, 0.7 g of isobutyl chloroformate was added to the mixture at-40° C., and stirred for 1 hour at -20° C. 1 g of2-(4-chlorobenzyloxy)-1-methylethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The obtained oilyresidue was purified by column chromatography on silica gel, thusobtaining 0.9 g of the desired product in the form of a colorless platedcrystal (yield: 48%).

SYNTHESIS EXAMPLE 24 Synthesis of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-methylthiophenoxy)ethyl]-L-valinamide (Compound No. 327)

3.4 g of N-methylpiperidine was added to a solution containing 7.5 g ofN-tert-butoxycarbonyl-L-valine dissolved in 100 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 4.7 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 6.8 g of1-methyl-2-(4-methylthiophenoxy)ethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous sodium sulfate and themethylene chloride was removed under reduced pressure. The obtained oilyresidue was purified by column chromatography on silica gel, thusobtaining 6.2 g of the desired product in the form of a colorlessprism-shaped crystal (yield: 46%).

SYNTHESIS EXAMPLE 25 Synthesis of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-methylsulfinylphenoxy)ethyl]-L-valinamide (Compound No.328)

1.5 g of m-chloroperbenzoic acid was added to a solution containing 3.0g of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-methylthiophenoxy)ethyl]-L-valinamide dissolved in 60 mlof methylene chloride, at 0° C. After the mixture was stirred for 5hours at room temperature, the reaction mixture was filtered. Thefiltrate was washed successively with a saturated aqueous solution ofpotassium carbonate and water, the organic layer was dried overanhydrous sodium sulfate and the methylene chloride was removed underreduced pressure. The obtained oily residue was purified by columnchromatography on silica gel, thus obtaining 1.7 g of the desiredproduct in the form of a colorless crystal (yield: 56%).

SYNTHESIS EXAMPLE 26 Synthesis of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-methylsulfonylphenoxy)ethyl]-L-valinamide (Compound No.329)

2.1 g of m-chloroperbenzoic acid was added to a solution containing 2.0g of N² -tert-butoxycarbonyl-N¹-[1-methyl-2-(4-methylthiophenoxy)ethyl]-L-valinamide dissolved in 50 mlof methylene chloride, at 0° C. After the mixture was stirred for 8hours at a reflux temperature, the reaction mixture was allowed to sitand cool naturally to room temperature and filtered. The filtrate waswashed successively with a saturated aqueous solution of potassiumcarbonate and water, the organic layer was dried over anhydrous sodiumsulfate and the methylene chloride was removed under reduced pressure.The obtained residue was purified by column chromatography on silicagel, thus obtaining 1.3 g of the desired product in the form of acolorless prism-shaped crystal (yield: 60%).

SYNTHESIS EXAMPLE 27 Synthesis of N¹-[2-(4-fluorophenylsulfinyl)-1-methylethyl]-N²-isopropoxycarbonyl-L-valinamide (Compound No. 354)

1.3 g of m-chloroperbenzoic acid was added to a solution containing 2.5g of N¹ -[2-(4-fluorophenylthio)-1-methylethyl]-N²-isopropoxycarbonyl-L-valinamide dissolved in 50 ml of methylenechloride, at 0° C. After the mixture was stirred for 5 hours at roomtemperature, the reaction mixture was filtered. The filtrate was washedsuccessively with a saturated aqueous solution of potassium carbonateand water, the organic layer was dried over anhydrous sodium sulfate andthe methylene chloride was removed under reduced pressure. The obtainedresidue was purified by column chromatography on silica gel, thusobtaining 1.8 g of the desired product in the form of a colorlessprism-shaped crystal (yield: 69%).

SYNTHESIS EXAMPLE 28 Synthesis of N¹-[2-(4-fluorophenylsulfonyl)-1-methylethyl]-N²-isopropoxycarbonyl-L-valinamide (Compound No. 355)

3.4 g of m-chloroperbenzoic acid was added to a solution containing 2.2g of N¹ -[2-(4-fluorophenylthio)-1-methylethyl]-N²-isopropoxycarbonyl-L-valinamide dissolved in 50 ml of methylenechloride, at 0° C. After the mixture was stirred for 8 hours at a refluxtemperature, the reaction mixture was allowed to sit and cool to roomtemperature, and then filtered. The filtrate was washed successivelywith a saturated aqueous solution of potassium carbonate and water, theorganic layer was dried over anhydrous sodium sulfate and the methylenechloride was removed under reduced pressure. The obtained residue waspurified by column chromatography on silica gel, thus obtaining 2.0 g ofthe desired product in the form of a white crystal (yield: 83%).

SYNTHESIS EXAMPLE 29 Synthesis of N² -isopropoxycarbonyl-N¹-[1-methyl-2-(2-methylphenylthio)ethyl]-L-valinamide (Compound No. 367)

1.9 g of N-methylpiperidine was added to a solution containing 3.9 g ofN-isopropoxycarbonyl-L-valine dissolved in 80 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 2.6 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 3.5 g of1-methyl-2-(2-methylphenylthio)ethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous sodium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 3.6 g ofthe desired product in the form of a white crystal (yield: 51%).

SYNTHESIS EXAMPLE 30 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl)-N²-(3-tetrahydrofuranyl)oxycarbonyl-L-valinamide (Compound No. 376)

1.0 g of N-methylmorpholine, and subsequently 0.7 g of3-tetrahydrofuranyl chloroformate were added to a suspension containing1.5 g of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamidehydrochloride suspended in 100 ml of methylene chloride at -20° C. Themixture was allowed to sit and warm naturally to room temperature andstirred for 2 hours at room temperature. Water was subsequently added tothe reaction mixture. After the dichloromethane layer was washed withwater, the organic layer was dried over anhydrous magnesium sulfate andthen the methylene chloride was removed under reduced pressure. Theresidue was purified by column chromatography on silica gel, thusobtaining 1.1 g of the desired product in the form of white powder(yield: 61%).

SYNTHESIS EXAMPLE 31 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(3-methylcyclohexyloxycarbonyl)-L-valinamid (Compound No. 379)

0.4 g of N-methylmorpholine, and subsequently 0.8 g of3-methylcyclohexyl chloroformate were added to a suspension containing1.0 g of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide suspendedin 50 ml of methylene chloride at -15° C. The mixture was allowed to sitand warm naturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 1.2 g of the desiredproduct in the form of a white crystal (yield: 80% ).

SYNTHESIS EXAMPLE 32 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-propargyloxycarbonyl-L-valinamide (Compound No. 381)

0.2 g of N-methylmorpholine, and subsequently 0.2 g of propargylchloroformate were added to a suspension containing 0.5 g of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide suspended in 30 ml ofmethylene chloride at -15° C. The mixture was allowed to sit and warmnaturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 0.5 g of the desiredproduct in the form of white powder (yield: 78%).

SYNTHESIS EXAMPLE 33 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(2-methoxy-1-methylethyl)oxycarbonyl-L-valinamide (Compound No. 383)

1.0 g of N-methylmorpholine, and subsequently 0.7 g of2-methoxy-1-methylethyl chloroformate were added to a suspensioncontaining 1.5 g of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamidesuspended in 150 ml of methylene chloride at -20° C. The mixture wasallowed to sit and warm naturally to room temperature and stirred for 2hours at room temperature. Water was subsequently added to the reactionmixture. After the methylene chloride layer was washed with water, theorganic layer was dried over anhydrous magnesium sulfate and then themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 0.37 gof the desired product in the form of a white plated crystal (yield:20%).

SYNTHESIS EXAMPLE 34 Synthesis of N¹-[2-(4-fluoro-N-methylanilino)-1-methylethyl]-N²-phenoxycarbonyl-L-valinamide (Compound No. 391)

1.6 g of N-methylpiperidine was added to a solution containing 3.9 g ofN-phenoxycarbonyl-L-valine dissolved in 80 ml of methylene chloride, at-20° C. After the mixture was stirred for 10 minutes at the sametemperature, 2.2 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 3.0 g of2-(4-fluoro-N-methylanilino)-1-methylethylamine was added to thismixture at -60° C., and then the reaction mixture was allowed to sit andwarm naturally to room temperature while being stirred, and was stirredfor 20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous sodium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 1.2 g ofthe desired product in the form of a white crystal (yield: 19%).

SYNTHESIS EXAMPLE 35 Synthesis of N² -(4-chlorophenoxycarbonyl)-N¹-[2-(4-cyanophenoxy-1-methylethyl]-L-valinamide (Compound Nos. 395 and396)

1.7 g of N-methylpiperidine was added to a solution containing 4.7 g ofN-(4-chlorophenoxycarbonyl)-L-valine dissolved in 250 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 2.3 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 3.0 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 15 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The obtained crude crystal was purifiedby column chromatography on silica gel, thus obtaining 0.4 g of thedesired product in the form of white powder. In addition, the powder waspurified by HPLC (YMC-063-15, hexane/ethyl acetate=55/45) to separatetwo fractions. One fraction possessing a short retention time was 0.17 gof white powder possessing 137°-140° C. of melting point (yield: 2%),and another fraction possessing a long retention time was 0.17 g ofwhite powder possessing a melting point of 174°-179° C. (yield: 2%).

SYNTHESIS EXAMPLE 36 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(2-nitrophenoxycarbonyl-L-valinamide (Compound No. 400)

1.3g of N-methylmorpholine, and subsequently 2.5 g of 2nitrophenylchloroformate were added to a suspension containing 3.4 g of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide suspended in 100 ml ofmethylene chloride at -20° C. The mixture was allowed to sit and warmnaturally to room temperature and stirred for 2 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 1.0 g of the desiredproduct in the form of a yellow plated crystal (yield: 18%).

SYNTHESIS EXAMPLE 37 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(4-fluorophenoxycarbonyl)-L-valinamide (Compound. No. 401)

1.2 g of N-methylpiperidine was added to a solution containing 3.0 g ofN-(4-fluorophenoxycarbonyl)-L-valine dissolved in 80 ml of methylenechloride, at -20° C. After the mixture was stirred for 15 minutes at thesame temperature, 1.6 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 2.3 g of(-)-2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The obtainedcrude crystal was purified by column chromatography on silica gel, thusobtaining 1.1 g of the desired product in the form of a white crystal(yield: 23% ).

SYNTHESIS EXAMPLE 38 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N²-(3,4-dimethylphenoxycarbonyl)-L-valinamide (Compound No. 403)

0.6 g of N-methylmorpholine, and subsequently 1.2 g of3,4-dimethylphenyl chloroformate were added to a suspension containing1.5 g of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide suspendedin 50 ml of methylene chloride at -15° C. The mixture was allowed to sitand warm naturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 1.7 g of the desiredproduct in the form of a white crystal (yield: 74%).

SYNTHESIS EXAMPLE 39 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(2-pyridyloxy)-1-methylethyl]-L-valinamide (Compound No. 409)

2.0 g of N-methylpiperidine was added to a solution containing 4.3 g ofN-tert-butoxycarbonyl-L-valine dissolved in 80 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 2.7 g of isobutyl chloroformate was added to the mixture at-40° C., and stirred for 1 hour at -20° C. 3.3 g of2-(2-pyridyloxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous sodium sulfate and the methylene chloride wasremoved under reduced pressure. The obtained crude crystal was purifiedby column chromatography on silica gel, thus obtaining 2.0 g of thedesired product in the form of colorless grains (yield: 28%).

SYNTHESIS EXAMPLE 40 Synthesis of N¹-[2-(5-chloro-2-pyridyloxy)-1-methylethyl]-N²-isopropyloxycarbonyl-L-valinamide (Compound No. 412)

0.8 g of N-methylmorpholine, and subsequently 0.5 g of isopropylchloroformate were added to a suspension containing 1.4 g of N¹-[2-(5-chloro-2-pyridyloxy)-1-methylethyl]-L-valinamide hydrochloridesuspended in 50 ml of methylene chloride at -15° C. The mixture wasallowed to sit and warm naturally to room temperature and stirred for 15hours at room temperature. Water was subsequently added to the reactionmixture. After the methylene chloride layer was washed with water, theorganic layer was dried over anhydrous magnesium sulfate and then themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 0.6 g ofthe desired product in the form of colorless grains (yield: 38%).

SYNTHESIS EXAMPLE 41 Synthesis of N¹-[2-(5-chloro-2-pyridyloxy)-1-methylethyl]-N²-phenoxycarbonyl-L-valinamide (Compound No. 413)

0.8 g of N-methylmorpholine, and subsequently 0.7 g of phenylchloroformate were added to a suspension containing 1.4 g of N¹-[2-(5-chloro-2-pyridyloxy)-1-methylethyl]-L-valinamide hydrochloridesuspended in 50 ml of methylene chloride at -15° C. The mixture wasallowed to sit and warm naturally to room temperature and stirred for 15hours at room temperature. Water was subsequently added to the reactionmixture. After the methylene chloride layer was washed with water, theorganic layer was dried over anhydrous magnesium sulfate and then themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 0.6 g ofthe desired product in the form of colorless grains (yield: 34%).

SYNTHESIS EXAMPLE 42 Synthesis of N¹-[2-(4-fluoro-N-methylanilino)-1-methylethyl]-N²-phenoxycarbonyl-L-isoleucinamide (Compound No. 422)

1.9 g of N-methylpiperidine was added to a solution containing 4.8 g ofN-phenoxycarbonyl-L-isoleucine dissolved in 80 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 2.6 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 3.5 g of2-(4-fluoro-N-methylanilino)-1-methylethylamine was added to thismixture at -60° C., and then the reaction mixture was allowed to sit andwarm naturally to room temperature while being stirred, and was stirredfor 20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous sodium sulfate and themethylene chloride was removed under reduced pressure. The obtainedcrude crystal was purified by column chromatography on silica gel, thusobtaining 1.1 g of the desired product in the form of a white crystal(yield: 13%).

SYNTHESIS EXAMPLE 43 Synthesis of N² -(ethylthio)carbonyl-N¹-[1-methyl-2-(4-nitrophenoxy)ethyl]-L-valinamide (Compound No. 432)

0.3 g of N-methylmorpholine, and subsequently 0.4 g of ethylchlorothioformate were added to a suspension containing 0.9 g of N¹-[1-methyl-2-(4-nitrophenoxy)ethyl]-L-valinamide suspended in 50 ml ofmethylene chloride at -15° C. The mixture was allowed to sit and warmnaturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 1.0 g of the desiredproduct in the form of yellow grains (yield: 79%).

SYNTHESIS EXAMPLE 44 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-leucinamide (Compound No. 455)

1.5 g of N-methylpiperidine was added to a solution containing 3.4 g ofN-tert-butoxycarbonyl-L-leucine dissolved in 60 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 2.0 g of isobutyl chloroformate was added to themixture at -40° C., and stirred for 1 hour at -20° C. 2.6 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for 15 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The obtained crude crystal was purifiedby column chromatography on silica gel, thus obtaining 5.1 g of thedesired product in the form of a colorless glutinous substance (yield:86%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               0.92          (6H, m)                                                         1.28, 1.32    (3H, d)                                                         1.39, 1.43    (9H, s)                                                         1.46, 1.65    (2H, m)                                                         1.65          (1H, m)                                                         3.98          (2H, m)                                                         4.06          (1H, m)                                                         4.35          (1H, m)                                                         4.91          (1H, br)                                                        6.46          (1H, br)                                                        6.97          (2H, d)                                                         7.57          (2H, dd)                                                 ______________________________________                                    

SYNTHESIS EXAMPLE 45 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-tert-leucinamide (Compound No.457)

1.7 g of N-methylpiperidine was added to a solution containing 4 g ofN-tert-butoxycarbonyl-L-tert-leucine dissolved in 50 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 2.4 g of isobutyl chloroformate was added to themixture at -40° C., and stirred for 1 hour at -20° C. 3.1 g of2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60°C., and then the reaction mixture was allowed to sit and warm naturallyto room temperature while being stirred, and was stirred for hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The obtained crude crystal was purifiedby column chromatography on silica gel, thus obtaining 3.9 g of thedesired product in the form of a colorless amorphous substance (yield:58%).

SYNTHESIS EXAMPLE 46 Synthesis of2-tert-butoxycarbonylamino-3-methyl-N-[2-(4-cyanophenoxy)-1-methylethyl]-3-butenicacid amide (Compound No. 460)

0.5 g of N-methylpiperidine was added to a solution containing 1.1 g of2-tert-butoxycarbonylamino-3-methyl-3-butenic acid dissolved in 40 ml ofmethylene chloride, at -20° C. After the mixture was stirred for 10minutes at the same temperature, 0.7 g of isobutyl chloroformate wasadded to the mixture at -40° C., and stirred for 1 hour at -20° C. 1.9 gof 2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The obtainedcrude crystal was purified by column chromatography on silica gel, thusobtaining 0.3 g of the desired product in the form of a colorlessglutinous substance (yield: 32%).

SYNTHESIS EXAMPLE 47 Synthesis ofN-[2-(4-cyanophenoxy)-1-methylethyl]-2-isopropoxycarbonylaminocyclopentylaceticacid amide (Compound No. 462)

0.4 g of N-methyhnorpholine, and subsequently 0.5 g of isopropylchloroformate were added to a suspension containing 1.2 g of2-amino-N-[2-(4-cyanophenoxy)-1-methylethyl]cyclopentylacetic acid amidesuspended in 40 ml of methylene chloride at -15° C. The mixture wasallowed to sit and warm naturally to room temperature and stirred for 15hours at room temperature. Water was subsequently added to the reactionmixture. After the methylene chloride layer was washed with water, theorganic layer was dried over anhydrous magnesium sulfate and then themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 1.4 g ofthe desired product in the form of a colorless plated crystal (yield:90%).

SYNTHESIS EXAMPLE 48 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N² -phenoxycarbonyl-L-norvalinamide(Compound No. 465)

0.5 g of N-methylmorpholine, and subsequently 0.8 g of phenylchloroformate were added to a suspension containing 1.4 g of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-norvalinamide suspended in 40 mlof methylene chloride at -15° C. The mixture was allowed to sit and warmnaturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 1.1 g of the desiredproduct in the form of a colorless plated crystal (yield: 57%).

SYNTHESIS EXAMPLE 49 Synthesis of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-N² -phenoxycarbonyl-L-leucinamide(Compound No. 466)

0.5 g of N-methylmorpholine, and subsequently 0.8 g of phenylchloroformate were added to a suspension containing 1.5 g of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-leucinamide suspended in 40 ml ofmethylene chloride at -15° C. The mixture was allowed to sit and warmnaturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed tinder reduced pressure. The residue was purifiedby column chromatography on silica gel, thus obtaining 1.5 g of thedesired product in the form of colorless powder (yield: 73%)

SYNTHESIS EXAMPLE 50 Synthesis of2-(4-chlorophenoxycarbonylamino)-N-[2-(4-cyanophenoxy)-1-methylethyl]cyclopentylaceticacid amide (Compound No. 471)

0.4 g of N-methylmorpholine, and subsequently 0.8 g of 4-chlorophenylchloroformate were added to a suspension containing 1.2 g of2-amino-N-[2-(4-cyanophenoxy)-1-methylethyl]cyclopentylacetic acid amidesuspended in 40 ml of methylene chloride at -15° C. The mixture wasallowed to sit and warm naturally to room temperature and stirred for 15hours at room temperature. Water was subsequently added to the reactionmixture. After the methylene chloride layer was washed with water, theorganic layer was dried over anhydrous magnesium sulfate and then themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 0.6 g ofthe desired product in the form of colorless grains (yield: 30%).

SYNTHESIS EXAMPLE 51 Synthesis of N² -benzyloxycarbonyl-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-(4-chlorophenyl)glycinamide(Compound No. 475)

0.4 g of N-methyhnorpholine, and subsequently 0.6 g of benzylchloroformate were added to a suspension containing 1.3 g of N¹-[2-(4-cyanophenoxy)-1-methylethyl]-(4-chlorophenyl)glycinamidesuspended in 40 ml of methylene chloride at -15° C. The mixture wasallowed to sit and warm naturally to room temperature and stirred for 15hours at room temperature. Water was subsequently added to the reactionmixture. After the methylene chloride layer was washed with water, theorganic layer was dried over anhydrous magnesium sulfate and then themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 1.2 g ofthe desired product in the form of colorless grains (yield: 70%).

SYNTHESIS EXAMPLE 52 Synthesis of N²-(1-cyano-1-methylethoxycarbonyl)-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide (Compound No. 476)

0.5 g of N-methylmorpholine, and subsequently 0.4 g of1-cyano-1-methylethyl chloroformate were added to a suspensioncontaining 0.7 g of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamidehydrochloride suspended in 50 ml of methylene chloride at -20° C. Themixture was allowed to sit and warm naturally to room temperature andstirred for 3 hours at room temperature. Water was subsequently added tothe reaction mixture. After the methylene chloride layer was washed withwater, the organic layer was dried over anhydrous magnesium sulfate andthen the methylene chloride was removed under reduced pressure. Theresidue was purified by column chromatography on silica gel, thusobtaining 0.6 g of the desired product in the form of colorless grains(yield: 71%).

SYNTHESIS EXAMPLE 53 Synthesis of N² -(2-chlorocyclohexyloxycarbonyl)-N¹-[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamide (Compound No. 477)

0.4 g of N-methylmorpholine, and subsequently 0.9 g of2-chlorocyclohexyl chloroformate were added to a suspension containing1.0 g of N¹ -[2-(4-cyanophenoxy)-1-methylethyl]-L-valinamidehydrochloride suspended in 50 ml of methylene chloride at -20° C. Themixture was allowed to sit and warm naturally to room temperature andstirred for 15 hours at room temperature. Water was subsequently addedto the reaction mixture. After the methylene chloride layer was washedwith water, the organic layer was dried over anhydrous magnesium sulfateand then the methylene chloride was removed under reduced pressure. Theresidue was purified by column chromatography on silica gel, thusobtaining 1.1 g of the desired product in the form of a white crystal(yield: 71%).

SYNTHESIS EXAMPLE 54 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-methylethyl]-L-valinamide(Compound No. 479)

2.0 g of N-methylpiperidine was added to a solution containing 5.6 g ofN-tert-butoxycarbonyl-L-valine dissolved in 100 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 2.7 g of isobutyl chloroformate was added to themixture at -40° C., and stirred for 1 hour at -20° C. 1.5 g of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-methylethylamine was addedto this mixture at -60° C., and then the reaction mixture was allowed tosit and warm naturally to room temperature, with stirring, and stirredfor 20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous sodium sulfate and themethylene chloride was removed under reduced pressure. The obtainedcrude crystal was purified by column chromatography on silica gel, thusobtaining 7.0 g of the desired product in the form of colorless grains(yield: 77%).

SYNTHESIS EXAMPLE 55 Synthesis of N¹-[1-(5-chloro-6-ethyl-4-pyrimidinyloxy)-2-propyl]-N²-isopropoxycarbonyl-L-valinamide (Compound No. 481)

0.34 g of N-methylpiperidine was added to a solution containing 0.7 g ofN-isopropoxycarbonyl-L-valine dissolved in 50 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 0.47 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 0.74 g of1-(5-chloro-6-ethyl-4-pyrimidinyloxy)-2-propylamine was added to thismixture at -60° C., and then the reaction mixture was allowed to sit andwarm naturally to room temperature while being stirred, and was stirredfor 20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous magnesium sulfate and themethylene chloride was removed under reduced pressure. The obtainedcrude crystal was purified by column chromatography on silica gel, thusobtaining 0.6 g of the desired product in the form of a whiteprism-shaped crystal (yield: 43%).

SYNTHESIS EXAMPLE 56 Synthesis ofN-tert-butoxycarbonyl-L-valyl-N-(4-chlorophenyl)-N-methyl-DL-alaninamide(Compound No. 490)

0.9 g of N-methylpiperidine was added to a solution containing 2.0 g ofN-tert-butoxycarbonyl-L-valine dissolved in 40 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 1.3 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 2.0 g of N¹ -(4-chlorophenyl)-N¹-methyl-DL-alaninamide was added to this mixture at -60° C., and thenthe reaction mixture was allowed to sit and warm naturally to roomtemperature while being stirred, and was stirred for 20 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed successively with a 5% aqueoussolution of sodium bicarbonate and water, the organic layer was driedover anhydrous magnesium sulfate and the methylene chloride was removedunder reduced pressure. The obtained crude crystal was purified bycolumn chromatography on silica gel, thus obtaining 3.4 g of the desiredproduct in the form of a colorless needle crystal (yield: 87%).

SYNTHESIS EXAMPLE 57 Synthesis ofN-isopropoxycarbonyl-L-isoleucyl-N-(4-cyanophenyl)-D-alaninamide(Compound No. 506)

0.26 g of N-methylpiperidine was added to a solution containing 0.57 gof N-isopropoxycarbonyl-L-isoleucine dissolved in 60 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 0.36 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 0.5 g of N¹-(4-cyanophenyl)-D-alaninamide was added to this mixture at -60° C., andthen the reaction mixture was allowed to sit and warm naturally to roomtemperature while being stirred, and was stirred for 20 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed successively with a 5% aqueoussolution of sodium bicarbonate and water, the organic layer was driedover anhydrous sodium sulfate and the methylene chloride was removedunder reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.5 g of the desiredproduct in the form of white powder (yield: 49%).

SYNTHESIS EXAMPLE 58 Synthesis ofN-cyclohexyloxycarbonyl-L-valyl-N-(4-cyanophenyl)-D-alaninamide(Compound No. 509)

0.6 g of N-methyhnorpholine, and subsequently 0.6 g of cyclopentylchloroformate were added to a suspension containing 1.0 g ofL-valyl-N-(4-cyanophenyl)alaninamide, hydrochloride suspended in 50 mlof methylene chloride at -20° C. The mixture was allowed to sit and warmnaturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 0.6 g of the desiredproduct in the form of a white crystal (yield: 49% ).

SYNTHESIS EXAMPLE 59 Synthesis ofN-phenoxycarbonyl-L-valyl-N-(4-chlorobenzyl)-DL-alaninamide (CompoundNo. 516)

0.55 g of N-methyhnorpholine, and subsequently 0.43 g of phenylchloroformate were added to a suspension containing 0.95 g ofL-valyl-N-(4-chlorobenzyl)-DL-alaninamide, hydrochloride suspended in 50ml of methylene chloride at -15° C. The mixture was allowed to sit andwarm naturally to room temperature and stirred for 15 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed with water, the organic layerwas dried over anhydrous magnesium sulfate and then the methylenechloride was removed under reduced pressure. The residue was purified bycolumn chromatography on silica gel, thus obtaining 0.9 g of the desiredproduct in the form of white powder (yield: 75%).

SYNTHESIS EXAMPLE 60 Synthesis of N-phenoxycarbonyl-L-valyl-DL-alaninephenyl ester (Compound No. 522)

0.24 g of N-methylpiperidine was added to a solution containing 0.57 gof N-phenoxycarbonyl-L-valine dissolved in 40 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 0.33 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 0.5 g of DL-alanine phenyl ester wasadded to this mixture at -60° C., and then the reaction mixture wasallowed to sit and warm naturally to room temperature while beingstirred, and was stirred for 20 hours at room temperature. Water wassubsequently added to the reaction mixture. After the methylene chloridelayer was washed successively with a 5% aqueous solution of sodiumbicarbonate and water, the organic layer was dried over anhydrousmagnesium sulfate and the methylene chloride was removed under reducedpressure. The residue was purified by column chromatography on silicagel, thus obtaining 0.2 g of the desired product in the form of whitepowder (yield: 20%).

SYNTHESIS EXAMPLE 61 Synthesis of N¹ -(4-cyanophenyl)-N²-(2-phenoxycarbonylamino)-(2S)-butyryl-D-alaninamide (Compound No. 524)

0.45 g of N-methylpiperidine was added to a solution containing 1.0 g of(2S)-2-phenoxycarbonylaminobutyric acid dissolved in 50 ml of methylenechloride, at -20° C. After the mixture was stirred for 10 minutes at thesame temperature, 0.61 g of isobutyl chloroformate was added to themixture, and stirred for 1 hour at -20° C. 0.85 g of N¹-(4-cyanophenyl)-D-alaninamide was added to this mixture at -60° C., andthen the reaction mixture was allowed to sit and warm naturally to roomtemperature while being stirred, and was stirred for 20 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed successively with a 5% aqueoussolution of sodium bicarbonate and water, the organic layer was driedover anhydrous magnesium sulfate and the methylene chloride was removedunder reduced pressure. The obtained crude crystal was purified bycolumn chromatography on silica gel, thus obtaining 0.8 g of the desiredproduct in the form of white powder (yield: 45%).

SYNTHESIS EXAMPLE 62 Synthesis ofN-isopropoxycarbonyl-L-valyl-N-(4-cyanophenyl)glycinamide (Compound No.526)

0.3 g of N-methylpiperidine was added to a solution containing 0.6 g ofN-isopropoxycarbonyl-L-valine dissolved in 40 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 0.4 g of isobutyl chloroformate was added to the n-fixture,and stirred for 1 hour at -20° C. 0.5 g of N¹-(4-cyanophenyl)glycinamide was added to this mixture at -60° C., andthen the reaction mixture was allowed to sit and warm naturally to roomtemperature while being stirred, and was stirred for 20 hours at roomtemperature. Water was subsequently added to the reaction mixture. Afterthe methylene chloride layer was washed successively with a 5% aqueoussolution of sodium bicarbonate and water, the organic layer was driedover anhydrous magnesium sulfate and the methylene chloride was removedunder reduced pressure. The residue was purified by columnchromatography on silica gel, thus obtaining 0.5 g of the desiredproduct in the form of colorless powder (yield: 49%).

SYNTHESIS EXAMPLE 63 Synthesis of N² -tert-butoxycarbonyl-N¹-(1,2-dimethyl-2-phenoxyethyl)-L-valinamide (Compound No. 602)

0.6 g of N-methylpiperidine was added to a solution containing 1.3 g ofN-tert-butoxycarbonyl-L-valine dissolved in 40 ml of methylene chloride,at -20° C. After the mixture was stirred for 15 minutes at the sametemperature, 0.8 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 1 g of1,2-dimethyl-2-phenoxyethylamine was added to this mixture at -60° C.,and then the reaction mixture was allowed to sit and warm naturally toroom temperature while being stirred, and was stirred for 20 hours atroom temperature. Water was subsequently added to the reaction mixture.After the methylene chloride layer was washed successively with a 5%aqueous solution of sodium bicarbonate and water, the organic layer wasdried over anhydrous magnesium sulfate and the methylene chloride wasremoved under reduced pressure. The obtained oily substance was purifiedby column chromatography on silica gel, thus obtaining 1.3 g of thedesired product in the form of a white glutinous substance (yield: 57%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               0.8-1.02      (6H, m)                                                         1.18-1.45     (15H, m)                                                        2.10          (1H, m)                                                         3.65-4.45     (3H, m)                                                         5.18          (1H, m)                                                         6.38          (1H, m)                                                         6.72-7.35     (5H, m)                                                  ______________________________________                                    

SYNTHESIS EXAMPLE 64 Synthesis of N² -tert-butoxycarbonyl-N¹-[2-(4-cyanophenoxy)-1,2-dimethylethyl]-L-valinamide (Compound No. 607)

0.5 g of N-methylpiperidine was added to a solution containing 1.1 g ofN-tert-butoxycarbonyl-L-valine dissolved in 60 ml of methylene chloride,at -20° C. After the mixture was stirred for 10 minutes at the sametemperature, 0.7 g of isobutyl chloroformate was added to the mixture,and stirred for 1 hour at -20° C. 1.0 g of2-(4-cyanophenoxy)-1,2-dimethylethylamine was added to this mixture at-60° C., and then the reaction mixture was allowed to sit and warmnaturally to room temperature while being stirred, and was stirred for20 hours at room temperature. Water was subsequently added to thereaction mixture. After the methylene chloride layer was washedsuccessively with a 5% aqueous solution of sodium bicarbonate and water,the organic layer was dried over anhydrous sodium sulfate and themethylene chloride was removed under reduced pressure. The residue waspurified by column chromatography on silica gel, thus obtaining 1.2 g ofthe desired product in the form of a colorless glassy substance (yield:61%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               0.79-1.03     (6H, m)                                                         1.15-1.46     (15H, m)                                                        2.03          (1H, m)                                                         3.63-4.72     (3H, m)                                                         5.06          (1H, m)                                                         6.30          (1H, m)                                                         6.83-7.60     (4H, m)                                                  ______________________________________                                    

SYNTHESIS EXAMPLE 65 Synthesis of N¹ -[2-(4-cyanophenoxy)propyl]-N²-phenoxycarbonyl-L-valinamide (Compound No. 750)

0.16 g of N-methylpiperidine was added to a suspension containing 0.25 gof N¹ -[2-(4-cyanophenoxy)propyl]-L-valinamide hydrochloride suspendedin 20 ml of methylene chloride, at -20° C. After the mixture was stirredfor 10 minutes at the same temperature, 0.13 g of phenyl chloroformatewas added drop by drop to the mixture, and then the reaction mixture wasallowed to sit and warm naturally to room temperature while beingstirred, and was stirred for 3 hours at room temperature. After themethylene chloride was removed under reduced pressure, the residue waspurified by column chromatography on silica gel, thus obtaining 0.2 g ofthe desired product in the form of a white glutinous substance (yield:63%).

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, δ)                                           ______________________________________                                               1.00          (6H, m)                                                         1.23          (3H, d)                                                         2.13          (1H, m)                                                         3.31          (1H, m)                                                         4.00          (2H, m)                                                         4.49          (1H, m)                                                         5.93          (1H, d)                                                         6.52          (1H, m)                                                         6.80-7.56     (9H, m)                                                  ______________________________________                                    

The agricultural or horticultural fungicide according to the presentinvention is a composition containing an amino acid amide derivativerepresented by Formula [I] as an active ingredient. In the case wherethe compounds according to the present invention are employed as anagricultural or horticultural fungicide, the compounds acting as theactive ingredient can be formulated appropriately, depending on thepurpose. The active ingredient is usually diluted in an inert liquid ora solid carrier, and a surfactant or the like is added thereto, ifnecessary. The mixture is then formulated in a known manner into, forexample, a fine powder, a wettable powder, an emulsifiable concentrate,granules, or the like.

Suitable examples of carriers employed in the formulation are solidcarriers such as talc, bentonite, clay, kaolin, diatomaceous earth,white carbon, vermiculite, slaked lime, siliceous sand, ammoniumsulfate, urea, or the like; and liquid carriers such as isopropylalcohol, xylene, cyclohexanone, methylnaphthalene, and the like.Illustrative examples of the surfactants and dispersants include saltsof dinaphthylmethanesulfonic acid, sulfate esters of alcohol,alkylarylsulfonic acid, and ligninesulfonic acid, polyoxyethylene glycolethers, polyoxyethylene alkyl aryl ethers, polyoxyethylenesorbitanmonoalkylates, and the like. Suitable examples of auxiliary agentsinclude carboxymethylcellulose, and the like. These preparations can beapplied directly, or after diluting the preparation to a suitableconcentration.

The agricultural or horticultural fungicide according to the presentinvention can be employed for a number of purposes: for example,treating seeds, spraying of stem and leaf portions, injection intoirrigation water, and applying to the soil. The proportion of the activeingredient is selected as needed. When formulated into a fine powder orgranules, 0.1% by weight to 20% by weight of the active ingredient ispreferred. For an emulsifiable concentrate or wettable powder, 5% byweight to 80% by weight of the active ingredient is adequate.

The rate of application of the agricultural or horticultural fungicideaccording to the present invention may vary depending on the type ofactive compound employed, the kind of the pest or disease to becontrolled, the nature of occurrence of the pest or disease, the degreeof damage, environmental conditions, the form of preparation to be used,and the like. When the agricultural or horticultural fungicide of thepresent invention is applied directly in the form of fine powder orgranules, it is recommended that the rate of application of the activeingredient be suitably chosen within the range of 0.1 g to 5 kg per 10ares, preferably, in the range of 1 g to I kg per 10 ares. In addition,when the fungicide of the present invention is in the form of a liquidsuch as an emulsifiable concentrate or a wettable powder, it isrecommended that the ratio for application of the active ingredient besuitably chosen within the range of 0.1 ppm to 10,000 ppm, andpreferably within the range of 10 ppm to 3,000 ppm.

The compounds according to the present invention in the formulationdescribed above can control plant diseases caused by fungi in theOomycetes, Ascomycetes, Deuteromycetes, and Basidiomycetes or otherpathogenic fungi. The fungi include, but are not limited to,Pseudoperonospora such as cucumber downy mildew (Pseudoperonosporacubensis), Phytophthora such as tomato late blight (Phytophthorainfestans), and Plasmopara such as grape downy mildew (Plasmoparaviticola).

The agricultural or horticultural fungicide according to the presentinvention may be employed alone or in combination with other fungicides,insecticides, herbicides, plant growth modifiers, fertilizers or thelike.

Next, the representative formulations are illustrated with reference tothe following Formulation Examples, wherein all "%" represent "percentby weight".

Formulation Example 1 Fine powder

2% of Compound No. 15, 5% of diatomaceous earth, and 93% of clay wereuniformly mixed and ground into a fine powder.

Formulation Example 2 Wettable powder

50% of Compound No. 16, 45% of diatomaceous earth, 2% of sodiumdinaphthylmethanedisulfonate, and 3% of sodium ligninsulfonate wereuniformly mixed and ground into a wettable powder.

Formulation Example 3 Emulsifiable concentrate

30% of Compound No. 19, 20% of cyclohexanone, 11% of polyoxyethylenealkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% ofmethylnaphthalene were uniformly dissolved, thus obtaining anemulsifiable concentrate.

Formulation Example 4 Granules

5% of Compound No. 101, 2% of sodium lauryl alcohol sulfonate, 5% ofsodium lignin sulfonate, 2% of carbomethylcellulose, and 86% of claywere mixed and ground. 20% of water was added to the ground mixture. Theresulting mixture was kneaded and formed into granules of 14 mesh to 32mesh by means of an extrusion granulator, and then dried into thedesired granules.

Effects of the Invention

The agricultural or horticultural fungicides according to the presentinvention exhibit high ability to control the growth or spread ofcucumber downy mildew (Pseudoperonospora cubensis), tomato late blight(Phytophthora infestans), and grape downy mildew (Plasmopara viticola),and are effective for potato late blight (Phytophthora infestans). Inaddition, the agricultural or horticultural fungicides according to thepresent invention not only exhibit the ability to prevent fungalinfection, but also exhibit the ability to eliminate pathogenic fungiafter it has invaded a host plant. Furthermore, the agricultural orhorticultural fungicides of the present invention are also characterizedin that they are not harmful chemicals and exhibit excellentcharacteristics such as systemic action, residual activity, andpersistence after rain-fall.

The effects of the compounds according to the present invention are nowillustrated with reference to the following Test Examples. ComparativeCompound X and Comparative Compound Y employed in the Test Examples arethe compounds disclosed as synthesis intermediates for drugs in JapanesePatent Application, First Publication, No. Sho 62-89696. TheseComparative Compounds were employed after being formulated in the samemanner as the compounds of the present invention to be tested.

Comparative Compound X: N² -tert-butoxycarbonyl-N¹-(2-phenoxyethyl)-D-alaninamide

Comparative Compound Y: N² -tert-butoxycarbonyl-N¹-(2-phenylthioethyl)-D-alaninamide

Test Example 1 Test on the Effect of Preventing Infection by CucumberDowny Mildew (Pseudoperonospora cubensis)

Cucumber seeds (variety: "Sagami hanjiro") were sown at a rate of 10seeds each in a square PVC (polyvinyl chloride) pot, wherein each sideis 9 cm wide. The seeds were allowed to grow in a greenhouse, for 7days, to the cotyledonous stage. A wettable powder prepared as inFormulation Example 2 was diluted with water to a concentration of 500ppm of the active ingredient, and the aqueous preparation obtained wasthen applied at a rate of 10 ml per pot to the cucumber seedlings attheir cotyledonous stage. After drying in the air, the plant wasinoculated with a spore suspension of cucumber downy mildew(Pseudoperonospora cubensis) fungi using a spray and then placed in amoist chamber at 22° C. for 24 hours, and then placed in a greenhouse.On the seventh day after the inoculation, the extent of lesion was ratedin accordance with the standards of evaluation as shown in Table 15 inorder to secure the preventive effects of the compounds according to thepresent invention. The results of the test are given in Table 16.

                  TABLE 15                                                        ______________________________________                                        Standard of evaluation:                                                                      Affected area                                                  Class A:       No lesions were observed                                       Class B:       Affected area is less than 25%                                 Class C:       Affected area is 25% or more and                                              less than 50%                                                  Class D:       Affected area is 50% or more                                   ______________________________________                                    

                  TABLE 16                                                        ______________________________________                                        Compound                                                                      No.            Evaluation                                                     ______________________________________                                         1             B                                                               2             A                                                               4             A                                                               6             A                                                               7             A                                                               8             B                                                               10            A                                                               13            A                                                               14            B                                                               16            A                                                               17            A                                                               18            B                                                               19            A                                                               23            A                                                               24            B                                                               26            B                                                               27            A                                                               29            A                                                               33            A                                                               42            A                                                               45            A                                                               54            B                                                               63            A                                                               77            A                                                               88            A                                                               98            A                                                              101            A                                                              104            A                                                              107            A                                                              108            A                                                              112            A                                                              114            A                                                              115            A                                                              116            A                                                              124            B                                                              129            A                                                              134            A                                                              135            A                                                              154            A                                                              157            A                                                              160            A                                                              163            A                                                              166            A                                                              169            A                                                              184            A                                                              193            A                                                              195            B                                                              204            B                                                              205            A                                                              208            A                                                              211            A                                                              212            A                                                              213            A                                                              214            A                                                              215            A                                                              216            A                                                              217            A                                                              219            A                                                              220            A                                                              221            A                                                              227            A                                                              228            A                                                              230            A                                                              231            A                                                              232            A                                                              235            A                                                              236            A                                                              238            A                                                              246            B                                                              323            A                                                              326            A                                                              327            A                                                              328            A                                                              329            B                                                              331            B                                                              333            B                                                              335            A                                                              336            A                                                              338            A                                                              339            A                                                              340            A                                                              341            A                                                              342            A                                                              343            A                                                              344            B                                                              345            A                                                              347            A                                                              348            B                                                              349            A                                                              350            B                                                              351            A                                                              352            A                                                              353            A                                                              354            A                                                              355            A                                                              356            A                                                              357            B                                                              358            A                                                              359            A                                                              360            A                                                              361            B                                                              362            B                                                              363            A                                                              364            B                                                              365            A                                                              366            A                                                              367            A                                                              368            A                                                              369            A                                                              370            A                                                              371            A                                                              372            A                                                              373            A                                                              374            A                                                              376            A                                                              377            A                                                              378            A                                                              379            A                                                              380            A                                                              381            A                                                              382            A                                                              383            A                                                              385            A                                                              386            A                                                              387            B                                                              388            A                                                              389            A                                                              390            A                                                              391            A                                                              392            A                                                              393            A                                                              394            A                                                              395            A                                                              397            A                                                              399            A                                                              401            A                                                              402            A                                                              403            A                                                              405            A                                                              408            A                                                              410            A                                                              411            B                                                              412            A                                                              413            A                                                              414            A                                                              416            A                                                              417            A                                                              418            A                                                              419            A                                                              421            A                                                              422            A                                                              423            A                                                              424            A                                                              425            A                                                              426            A                                                              427            A                                                              429            A                                                              430            A                                                              431            A                                                              432            A                                                              439            A                                                              440            A                                                              451            A                                                              452            A                                                              453            A                                                              455            A                                                              456            A                                                              462            A                                                              465            A                                                              466            A                                                              467            A                                                              468            A                                                              471            B                                                              477            A                                                              482            A                                                              486            A                                                              492            A                                                              493            A                                                              495            A                                                              496            B                                                              499            B                                                              502            A                                                              506            A                                                              508            A                                                              509            A                                                              510            A                                                              511            A                                                              512            A                                                              513            A                                                              517            A                                                              519            A                                                              523            A                                                              525            A                                                              605            A                                                              606            A                                                              607            A                                                              708            A                                                              768            A                                                              770            A                                                              Comparative    D                                                              Example X                                                                     Comparative    D                                                              Example Y                                                                     ______________________________________                                    

Test Example 2 Test on the Effect of Treating Infection by CucumberDowny Mildew (Pseudoperonospora cubensis)

Cucumber seeds (variety: "Sagami hanjiro") were sown at a rate of 10seeds each in a square PVC (polyvinyl chloride) pot, wherein each sideis 9 cm wide. The seeds were allowed to grow in a greenhouse, for 7days, to the cotyledonous stage. The seedlings were inoculated with aspore suspension of cucumber downy mildew (Pseudoperonospora cubensis)fungi and then placed in a moist chamber at 22° C. for 24 hours. Afterdrying in the air, a wettable powder prepared as in Formulation Example2 was diluted with water to a concentration of 500 ppm of the activeingredient, and the aqueous preparation obtained was then applied at arate of 10 ml per pot to the cucumber seedlings. The seedlings were thenplaced in a green house. On the seventh day after the inoculation, theextent of lesions was rated in accordance with the standards ofevaluation shown in Table 15 in order to secure the effect of treatingwith the compounds according to the present invention. The results ofthe test are given in Table 17.

                  TABLE 17                                                        ______________________________________                                        Compound                                                                      No.            Evaluation                                                     ______________________________________                                         4             B                                                               10            A                                                               13            A                                                               16            A                                                               19            B                                                               29            A                                                               33            A                                                               42            A                                                               45            A                                                               54            B                                                               63            A                                                               77            A                                                               88            B                                                              104            A                                                              107            A                                                              108            B                                                              114            B                                                              115            A                                                              116            A                                                              124            A                                                              129            B                                                              134            A                                                              135            A                                                              154            A                                                              157            A                                                              160            A                                                              163            A                                                              184            B                                                              212            A                                                              213            A                                                              215            A                                                              216            B                                                              219            A                                                              220            B                                                              221            A                                                              228            B                                                              230            B                                                              231            A                                                              232            A                                                              238            A                                                              333            A                                                              335            A                                                              336            A                                                              340            B                                                              341            B                                                              342            A                                                              345            A                                                              348            B                                                              349            A                                                              351            A                                                              352            A                                                              353            A                                                              354            A                                                              355            A                                                              356            A                                                              358            A                                                              360            B                                                              365            A                                                              367            B                                                              368            A                                                              369            A                                                              371            A                                                              374            A                                                              376            A                                                              378            A                                                              381            B                                                              382            A                                                              383            A                                                              385            A                                                              386            A                                                              388            B                                                              394            A                                                              395            A                                                              397            A                                                              399            A                                                              401            A                                                              402            B                                                              405            B                                                              414            A                                                              416            A                                                              417            A                                                              418            A                                                              419            B                                                              423            A                                                              424            A                                                              425            A                                                              427            A                                                              429            A                                                              439            A                                                              451            A                                                              452            A                                                              453            A                                                              455            A                                                              456            A                                                              462            A                                                              465            A                                                              466            A                                                              467            B                                                              468            A                                                              477            B                                                              486            B                                                              492            A                                                              495            A                                                              499            B                                                              502            A                                                              506            A                                                              508            A                                                              509            A                                                              513            A                                                              517            A                                                              519            B                                                              523            A                                                              606            A                                                              607            B                                                              708            A                                                              768            B                                                              770            B                                                              Comparative    D                                                              Example X                                                                     Comparative    D                                                              Example Y                                                                     ______________________________________                                    

Test Example 3 Test on the Effect of Preventing Infection by Tomato LateBlight (Phytophthora infestans)

One tomato seedling (variety: "Ponterosa") was transplanted into eachporcelain pot (diameter: 12 cm) and grown in a greenhouse. A wettablepowder prepared as in Formulation Example 2 was diluted with water to aconcentration of 500 ppm of the active ingredient, and the aqueouspreparation obtained was then applied at a rate of 20 ml per pot to thetomato seedlings at their 6- or 7-leaf stage. After drying in the air,the plant was inoculated with a zoosporangium suspension of tomato lateblight (Phytophthora infestans) fungi and then placed in a moist chamberat 22° C. On the fourth day after the inoculation, index of incidencewas determined based on the size of the affected area as shown in Table18. The degree of damage was calculated according to Equation (1) andthe index of incidence and the ability to prevent the disease(controlling activity) was calculated according to Equation (2). Theresults are shown in Table 19.

                  TABLE 18                                                        ______________________________________                                        Incidence Index                                                                             Affected Area                                                   ______________________________________                                        0             No lesions                                                      1             Less than 5%                                                    2             5% or more and less than 33.3%                                  3             33.3% or more and less than 66.6%                               4             66.6% or more                                                   ______________________________________                                         ##EQU1##

                  TABLE 19                                                        ______________________________________                                                       Controlling                                                    Compound       Activity                                                       No.            (%)                                                            ______________________________________                                         2             100                                                             4             100                                                             6             100                                                             7             100                                                             10            100                                                             13            100                                                             16            100                                                             17            100                                                             19            100                                                             23            100                                                             27            100                                                             29            100                                                             33            100                                                             42            100                                                             45            100                                                             63            100                                                             77            100                                                             88            100                                                             98            100                                                            101            100                                                            104            100                                                            107            100                                                            108            100                                                            112            100                                                            115            100                                                            116            100                                                            129            100                                                            134            100                                                            135            100                                                            154            100                                                            157            100                                                            160            100                                                            163            100                                                            166            100                                                            169            100                                                            184            100                                                            193            100                                                            213            100                                                            215            100                                                            217            100                                                            220            100                                                            221            100                                                            228            100                                                            231            100                                                            232            100                                                            235            100                                                            238            100                                                            323            100                                                            326            100                                                            336            100                                                            345            100                                                            352            100                                                            356            100                                                            359            100                                                            360            100                                                            364            100                                                            365            100                                                            369            100                                                            371            100                                                            372            100                                                            373            100                                                            374            100                                                            378            100                                                            379            100                                                            380            100                                                            381            100                                                            382            100                                                            386            100                                                            388            100                                                            390            100                                                            391            100                                                            393            100                                                            394            100                                                            395            100                                                            397            100                                                            399            100                                                            401            100                                                            402            100                                                            403            100                                                            404            100                                                            405            100                                                            408            100                                                            414            100                                                            417            100                                                            418            100                                                            423            100                                                            424            100                                                            427            100                                                            430            100                                                            439            100                                                            440            100                                                            451            100                                                            462            100                                                            465            100                                                            466            100                                                            467            100                                                            477            100                                                            482            100                                                            492            100                                                            495            100                                                            502            100                                                            508            100                                                            509            100                                                            513            100                                                            519            100                                                            523            100                                                            605            100                                                            606            100                                                            607            100                                                            708            100                                                            768            100                                                            770            100                                                            Comparative     0                                                             Example X                                                                     Comparative     0                                                             Example Y                                                                     ______________________________________                                    

Test Example 4 Test on the Effect of Preventing Infection by Grape DownyMildew (Plasmopara viticola)

Grape rooted cuttings (variety: "Kyoho"), each grown from a cutting andpruned, was grown in a porcelain pot (diameter: 12 cm) and maintained ina greenhouse. A wettable powder prepared as in Formulation Example 2 wasdiluted with water to a concentration of 500 ppm of the activeingredient, and the aqueous preparation obtained was then applied at arate of 20 ml per pot to the grape seedlings at their 4- or 5-leafstage. After drying in the air, the plant was inoculated with azoosporangium suspension of grape downy mildew (Plasmopara viticola)fungi and then placed in a moist chamber at 22° C. for 24 hours. On theseventh day in the greenhouse after the inoculation, the plant was againplaced in a moist chamber at 22° C. for 24 hours to cultivateconidiospores. The incidence area where conidiospores grew on each leafwas examined and the incidence index determined according to thestandards shown in Table 18. The degree of damage was calculatedaccording to Equation (1) and the incidence index and the ability toprevent the disease (controlling activity) was calculated according toEquation (2). The results of the test are shown in Table 20.

                  TABLE 20                                                        ______________________________________                                                       Controlling                                                    Compound       Activity                                                       No.            (%)                                                            ______________________________________                                         2             100                                                             4             100                                                             6             100                                                             7             100                                                             10            100                                                             13            100                                                             16            100                                                             17            100                                                             19            100                                                             23            100                                                             27            100                                                             29            100                                                             33            100                                                             42            100                                                             45            100                                                             63            100                                                             77            100                                                             88            100                                                             98            100                                                            101            100                                                            104            100                                                            107            100                                                            108            100                                                            112            100                                                            115            100                                                            116            100                                                            129            100                                                            134            100                                                            135            100                                                            154            100                                                            157            100                                                            160            100                                                            163            100                                                            166            100                                                            169            100                                                            184            100                                                            193            100                                                            213            100                                                            215            100                                                            217            100                                                            220            100                                                            221            100                                                            228            100                                                            231            100                                                            232            100                                                            235            100                                                            238            100                                                            323            100                                                            326            100                                                            336            100                                                            345            100                                                            352            100                                                            356            100                                                            359            100                                                            360            100                                                            364            100                                                            365            100                                                            369            100                                                            371            100                                                            372            100                                                            373            100                                                            374            100                                                            378            100                                                            379            100                                                            380            100                                                            381            100                                                            382            100                                                            386            100                                                            388            100                                                            390            100                                                            391            100                                                            393            100                                                            394            100                                                            395            100                                                            397            100                                                            399            100                                                            401            100                                                            402            100                                                            403            100                                                            404            100                                                            405            100                                                            408            100                                                            414            100                                                            417            100                                                            418            100                                                            423            100                                                            424            100                                                            427            100                                                            430            100                                                            439            100                                                            440            100                                                            451            100                                                            462            100                                                            465            100                                                            466            100                                                            467            100                                                            477            100                                                            482            100                                                            492            100                                                            495            100                                                            502            100                                                            508            100                                                            509            100                                                            513            100                                                            519            100                                                            523            100                                                            605            100                                                            606            100                                                            607            100                                                            708            100                                                            768            100                                                            770            100                                                            Comparative     0                                                             Example X                                                                     Comparative     0                                                             Example Y                                                                     ______________________________________                                    

What is claimed is:
 1. An amino-acid amide represented by the formula:##STR1270## wherein R¹ represents a lower alkyl group (optionally havingat least one same or different substituent selected from the groupconsisting of a halogen atom, an alkoxy group, and a cyano group),alower alkenyl group, a lower alkynyl group, a cycloalkyl group(optionally having at least one same or different substituent selectedfrom the group consisting of methyl group and a halogen atom), acycloalkylalkyl group, a cycloalkenyl group, an alkylene oxide group, anaralkyl group (optionally having at least one same or differentsubstituent selected from the group consisting of a methyl group, acyano group, and a nitro group), a phenyl group (optionally having atleast one same or different substituent selected from the groupconsisting of a halogen atom, a lower alkyl group which may besubstituted with a same or different halogen atom, a lower alkoxy groupwhich may be substituted with a same or different halogen atom, a cyanogroup, and a nitro group), or a heterocyclic group, R² represents anethyl group, an n-propyl group, an isopropyl group, an isobutyl group, asec-butyl group, a tert-butyl group, an alkenyl group, a cycloalkylgroup, a phenyl group (optionally having at least one substituent ofhalogen atom), R³ represents a hydrogen atom or a lower alkyl group, R⁴represents a hydrogen atom, a lower alkyl group, or a cyano group, R⁵,R⁶, and R⁷ independently represent a hydrogen atom or a lower alkylgroup, R⁸ represents a hydrogen atom, a lower alkyl group, an aralkylgroup, a phenyl group, an alkoxycarbonyl group, or a cyano group, Z¹ andZ² independently represent an oxygen atom or a sulfur atom, Z³representsan oxygen atom, a group N--R¹⁰ (wherein R¹⁰ represents ahydrogen atom, a methyl group, a methylcarbonyl group, a phenylcarbonylgroup, a methoxycarbonyl group, or a methoxymethyl group), a sulfinylgroup, a sulfonyl group, a group COO, a group CONR¹¹ (wherein R¹¹represents a hydrogen atom or a lower alkyl group), Q representsa phenylgroup (optionally having at least one same or different substituentselected from the group consisting of a halogen atom, a lower alkylgroup which may be substituted with at least one same or differenthalogen atom, a lower alkoxy group which may be substituted with a sameor different halogen atom, a cyano group, a nitro group, a loweralkoxycarbonyl group, a methylsulfonyl group, a methylsulfinyl group, amethylthio group which may be substituted with a halogen atom, adimethylamino group, a phenylsulfonyl group, a acyl group, and a phenylgroup), m represents an integer from 0 to 2, and n represents 0 or
 1. 2.An amino-acid amide represented by the formula: ##STR1271## wherein R¹represents a lower alkyl group (optionally having at least one same ordifferent substituent selected from the group consisting of a halogenatom, an alkoxy group, and a cyano group),a lower alkenyl group, a loweralkynyl group, a cycloalkyl group (optionally having at least one sameor different substituent selected from the group consisting of methylgroup and a halogen atom), a cycloalkylalkyl group, a cycloalkenylgroup, an alkylene oxide group, an aralkyl group (optionally having atleast one same or different substituent selected from the groupconsisting of a methyl group, a cyano group, and a nitro group), aphenyl group (optionally having at least one same or differentsubstituent selected from the group consisting of a halogen atom, alower alkyl group which may be substituted with a same or differenthalogen atom, a lower alkoxy group which may be substituted with a sameor different halogen atom, a cyano group, and a nitro group), or aheterocyclic group, R² represents an ethyl group, an n-propyl group, anisopropyl group, an isobutyl group, a sec-butyl group, a tert-butylgroup, an alkenyl group, a cycloalkyl group, a phenyl group (optionallyhaving at least one substituent of halogen atom), R³ represents ahydrogen atom or a lower alkyl group, R⁴ represents a hydrogen atom, alower alkyl group, or a cyano group, R⁵, R⁶, and R⁷ independentlyrepresent a hydrogen atom or a lower alkyl group, R⁸ represents ahydrogen atom, a lower alkyl group, an aralkyl group, a phenyl group, analkoxycarbonyl group, or a cyano group, Z¹ and Z² independentlyrepresent an oxygen atom or a sulfur atom, Q representsa phenyl grouphaving at least one same or different substituent selected from thegroup consisting of a halogen atom, a lower alkyl group which may besubstituted with at least one same or different halogen atom, a loweralkoxy group which may be substituted with a same or different halogenatom, a cyano group, a nitro group, a lower alkoxycarbonyl group, amethylsulfonyl group, a methylsulfinyl group, a methylthio group whichmay be substituted with a halogen atom, a dimethylamino group, aphenylsulfonyl group, a acyl group, and a phenyl group, and m representsan integer from 0 to
 2. 3. An amino-acid amide as recited in claim 1,which is represented by the formula: ##STR1272## wherein R¹ representsan isopropyl group, a tert-butyl group, a cyclopentyl group, or a phenylgroup (optionally having at least one same or different substituentselected from the group consisting of a halogen atom, a methyl group, amethoxy group, and a nitro group), andX represents a halogen atom, acyano group, or a nitro group.
 4. An amino-acid amide as recited inclaim 1, which is represented by the formula: ##STR1273## wherein R¹represents an isopropyl group, a tert-butyl group, a cyclopentyl group,a cyclohexyl group which may be substituted with a methyl group, or aphenyl group (optionally having at least one same or differentsubstituent selected from the group consisting of a halogen atom, amethyl group, a methoxy group, a trifluoromethyl group, atrifluoromethoxy group, and a nitro group), andX represents a halogenatom, a cyano group, or a nitro group.
 5. An amino-acid amide as recitedin claim 1, which is represented by the formula: ##STR1274## wherein R¹represents an isopropyl group, a tert-butyl group, a cyclopentyl group,or a phenyl group (optionally having at least one same or differentsubstituent selected from the group consisting of a halogen atom, amethyl group, a methoxy group, and a nitro group), andX represents ahalogen atom, a cyano group, or a nitro group.
 6. An amino-acid amide asrecited in claim 1, which is represented by the formula: ##STR1275##wherein R¹ represents a C₁ ˜C₆ alkyl group, a C₃ ˜C₈ cycloalkyl group,or a phenyl group (optionally having at least one substituent halogenatom),R² represents an ethyl group, an isopropyl group, or a sec-butylgroup, R⁴ represents a hydrogen atom or a C₁ ˜C₃ alkyl group, Z³represents a group COO, a group CONR¹¹ (wherein R¹¹ represents ahydrogen atom or a C₁ ˜C₃ alkyl group), Q represents a phenyl group(optionally having at least one same or different substituent selectedfrom the group consisting of a halogen atom, a C₁ ˜C₃ alkyl group, a C₁˜C₃ alkoxy group, and a cyano group), and n represents 0 or
 1. 7. Anagricultural or horticultural fungicidal composition which includes aneffective amount of an amino-acid amide as recited in claim
 1. 8. Anagricultural or horticultural fungicidal composition which includes aneffective amount of an amino-acid amide as claimed in claim
 1. 9. Anagricultural or horticultural fungicidal composition which includes aneffective amount of an amino-acid amide as claimed in claim 2.